EP1155111B1 - Method for producing rapidly disintegrating washing and cleaning agent shaped bodies - Google Patents

Abstract

The invention relates to washing and cleaning agent shaped bodies which are characterized by having both a high degree of hardness and thus stability during transport and handling as well as excellent disintegration properties. The inventive shaped bodies can be produced using a known tabletting process in which the premix to be compacted has a temperature of less than 20 DEG C immediately before compaction.

Description

The present invention relates to a process for the production of moldings, the have washing and cleaning properties. In particular, the invention relates a process for the preparation of detergent tablets for textile washing in a household washing machine, briefly referred to as detergent tablets become.

Commercially available detergents and cleaners are nowadays in the form of liquid products or solids offered. In the latter form of supply one distinguishes conventional Powders or concentrates, for example, by granulation or extrusion are available. Compared to the conventional powders have concentrated washing and Cleaning agent on the advantage that operated a reduced packaging costs must be and less volume must be dosed per wash. Also will be Reduced transport and storage costs due to the reduced package sizes. The highly concentrated form, in the detergents and cleaners currently in some Countries are offered in the market, are pressed detergent tablets. While water softeners and automatic dishwashing detergents in this supply form are widespread, appear in textile detergents a variety of problems that have hitherto resisted widespread dissemination and consumer acceptance. Due to the significantly higher surfactant contents are usually the offer form of the molding Exploited problems still potentiated. Particularly problematic are detergent tablets, which contain alkoxylated nonionic surfactants, as this class of surfactants Actively affects the solubility of the tablets - on the other hand are just these Surfactants expressly desired because of their high detergency.

In particular, the dichotomy between a sufficiently hard molded body and a sufficient fast disintegration time is a central problem. Since sufficiently stable, i. Shaped and break-resistant molded body produced only by relatively high compression pressures can be, it comes to a strong compression of the molding constituents and to a consequent delayed disintegration of the molding 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 continues to have the Disadvantage that usual washing and cleaning agent tablets do not have the Einspülkammer rinse with household washing machines as the tablets are not in sufficiently fast time to disintegrate into secondary particles that are small enough to out of Einspülkammer to be flushed into the washing drum.

To solve this problem, various approaches exist in the prior art. Next The use of special ingredients to promote disintegration will also be used Coating individual ingredients or the entire tablet proposed. These solutions approach the problem in a sense "from the recipe side", i. it certain ingredients are used or the tablet or parts of it by additives refined. In addition to these "chemical" solutions, there are also proposed solutions for the said problem, which is carried out regardless of the recipe can be. These "physical" approaches usually concern certain embodiments of tabletting machines or other process parameters, wherein the Pressing pressure is at the center of interest. Also proposed is the screening of the compressing premixes on certain grain fractions, regardless of the Composition of the premix advantageous properties of the moldings result should.

Thus, EP-A-0 466 484 (Unilever) discloses detergent tablets in which the premix to be compressed has particle sizes between 200 and 1200 μm, the upper and lower limits of the particle sizes differing by not more than 700 μm. About the surface treatment of individual ingredients nothing is carried out in this document.

Also, EP-A-0 522 766 (Unilever) relates to molded articles of a compacted particulate detergent composition containing surfactants, builders and disintegration aids (for example, cellulose-based) wherein at least a portion of the particles are coated with the disintegrating agent containing both binder and binder also shows disintegration effect when dissolving the moldings in water. This document also points to the general difficulty to produce moldings with adequate stability at the same time good solubility. The particle size in the mixture to be compressed should be above 200 microns, with the upper and lower limits of the individual particle sizes should not differ by more than 700 microns.

DE 40 10 533 (Henkel KGaA) discloses a process for the production of compacts from precompressed granules. In this case, the granules produced in a first stage by extrusion and dicing are optionally mixed with other ingredients and excipients and tabletted. The proportion of precompacted granules on the compacts in this document is up to 100%. A pretreatment of the optionally used Zumischkomponenten is not disclosed.

European Patent Application EP 711 828 (Unilever) claims a process for making laundry detergent tablets by compressing a particulate composition containing a binder. The melting point of the binder should be between 35 and 90 ° C and the compression at temperatures below the melting point, but above 28 ° C. So this font combines a "chemical" with a "physical" approach.

The "physical" approaches described above have the advantage that they both independently of the composition of the premix and independently of Type of tabletting machine used can be realized. This allows the manufacturer both in the composition of its detergent tablets as well as the acquisition or use of its machinery other framework conditions take greater account of it without being subject to any additional restrictions. Nevertheless, the detergent tablets prepared according to the documents mentioned have so far still disadvantages: Although they have a sufficient hardness, but often have Decay rates, the dosage via a dispensing chamber of a Do not allow household washing machine. In the cited documents of the prior Technique becomes dissolution times of less than 10 minutes and residue levels below 50% as well wherein such values for the use of detergent tablets on the Einspülkammer are completely inadequate.

The present invention was based on the object, a process for the preparation of detergent tablets to enable molding produce, which are free of the disadvantages mentioned. It should be on simple and highly reproducible way washing and cleaning agent moldings are produced can have a high hardness, but still by a fast Decay rate and also on the Einspülkammer of Household washing machines can be used. This should the expert the greatest possible Freedom of choice regarding the composition and selection of presses.

It has now been found that detergent tablets with the mentioned produce advantageous properties, if the pre-mixes to be compressed cool and tableted at lower temperatures.

The invention relates to a process for the preparation of washing and Detergent tablets by shaping pressing in a conventional manner, in the temperature of the premix to be compressed immediately before pressing below 15 ° C.

It is preferred in the context of the present invention, when the to be pressed Premix immediately before tableting has a temperature that significantly is below 15 ° C. Process variants according to the invention therefore become so stated that the premix to be compressed immediately before pressing a Temperature below 13 ° C and in particular below 10 ° C.

It goes without saying that premixing is also possible at temperatures of 14 ° C or 12 ° C or 11 ° C or 9 ° C or 8 ° C or 7 ° C or 6 ° C or 5 ° C or 4 ° C or 3 ° C or 2 ° C or 1 ° C or 0 ° C, according to the invention possible. Also the compression of Premixes with temperatures below freezing is possible according to the invention, Examples are temperatures of -1 ° C, -2 ° C, -3 ° C, -4 ° C, -5 ° C, -6 ° C, -7 ° C, -8 ° C, -9 ° C, -10 ° C, -11 ° C, -12 ° C, -13 ° C, -14 ° C, -15 ° C, -16 ° C, -17 ° C, -18 ° C, -19 ° C or -20 ° C called, wherein the premix can also have lower temperatures.

In preferred embodiments of the method according to the invention that includes Pressing premix of surfactant-containing granules (e) and others Treatment components. The preparation of surfactant-containing granules can by usual technical granulation processes such as compaction, extrusion, Mixer granulation, pelleting or fluidized bed granulation done. It is there for the later washing and cleaning product molding advantageous when the to be pressed Premix has a bulk density that comes close to the conventional compact detergent. In particular, it is preferred that the premix to be compressed has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l having.

The surfactant-containing granules are sufficient in preferred process variants Teilchengrößenkriterien. Thus, methods according to the invention are preferred in which the surfactant-containing granules particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, more preferably between 400 and 1600 microns and in particular between 600 and 1400μm.

In addition to the active substances (anionic and / or nonionic and / or cationic and / or amphoteric surfactants), the surfactant granules preferably also contain excipients, which particularly preferably originate from the group of builders. Particularly advantageous Processes are characterized in that the premix to be compressed containing surfactant-containing granules which anionic and / or nonionic surfactants and Contains builders and the total surfactant content of 5 to 60 wt .-%, preferably 10 up to 50% by weight and in particular 15 to 40% by weight, in each case based on the surfactant granules, is.

For the development of the washing performance, the surfactant granules contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic Surfactants, where anionic surfactants for economic reasons and because of their Power spectrum are clearly preferred.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation 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. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty 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 these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also, 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

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

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

As further anionic surfactants are particularly soaps into consideration. Suitable are 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
The anionic surfactants, including the soaps, may 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 present 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, washing and cleaning agent tablets are used preferably, the 5 to 50 wt .-%, preferably 7.5 to 40 wt .-% and in particular 10 to 20 wt .-% anionic surfactant (s), in each case based on the molding body weight.

When selecting the anionic surfactants used in the detergent tablets according to the invention are used, the freedom of formulation are none to be observed in the way. Preferred detergent tablets However, they have a soap content of 0.2% by weight, based on the total weight of the molding, exceeds. Preferably used anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred washing and Detergent tablets 2 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular From 5 to 10% by weight of fatty alcohol sulphate (e), in each case based on the molding weight, contain.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. 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.

Another class of preferred nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as they are for example, in Japanese Patent Application JP 58/217598 , or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533 .

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G) _z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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.

Preference is given to using linear alkyl polyglucosides, ie alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The detergent tablets according to the invention can preferably alkylpolyglycosides contained, wherein contents of the moldings to APG over 0.2 wt .-%, based on the entire molding, are preferred. Particularly preferred washing and Detergent tablets contain APG in amounts of from 0.2 to 10% by weight, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.

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 alkanolamide may be suitable. The amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, in particular not more than 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 Zukkers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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 (II)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with 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 residue.

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

As already mentioned above, the nonionic and anionic surfactants can over the different ways in the detergent tablets according to the invention be incorporated. You can, for example, the pre-mix to be pressed be added in solid form, or in liquid form from the premix be sprayed on. It has proved to be advantageous to prepare surfactant granules which blended with other powdered components to be tabletted premix and be pressed. According to the invention, washing and cleaning agent tablets are used preferably containing the surfactants in the form of a surfactant-containing granules, that in amounts of 40 to 95 wt .-%, preferably from 45 to 85 wt .-% and in particular from 55 to 75 wt .-%, each based on the molding weight, in the moldings is included.

To the desired amount of washing-active substance in the detergent tablets process variants are preferred in which the premix contains a surfactant-containing granules, the surfactant contents of 5 to 60 wt .-%, preferably from 10 to 50 wt .-% and in particular from 15 to 40 wt .-%, each based on the Weight of the surfactant granules having (see above). In particular washing and cleaning agent shaped bodies, in which the content of the surfactant granules of anionic surfactants From 5 to 45% by weight, preferably from 10 to 40% by weight and in particular from 15 to 35% by weight, in each case based on the weight of the surfactant granules, and washing and cleaning agent tablets, in which the content of surfactant granules of nonionic surfactants From 1 to 30% by weight, preferably from 5 to 25% by weight and in particular from 7.5 to 20% by weight, in each case based on the weight of the surfactant granules, are preferred according to the invention.

To obtain storage-stable and free-flowing surfactant granules, it is preferred if in the preparation of the surfactant granules carriers are added, the surfactant granules So contain builders. Other ingredients of detergents and cleaners, especially so-called small components such as optical brighteners, polymers, Defoamers, phosphonates, dyes and fragrances can form part of the surfactant granules be. These substances are described below.

In the second step of the process according to the invention, the surfactant granules with further Ingredients of detergents and cleaners to a compressible premix mixed and then tabletted. Here, according to the invention, the production of Detergent tablets preferred so that preferred variants of the method according to the invention characterized in that the proportion of surfactant-containing granules on pressing premix and thus to the washing and cleaning agent moldings 40th to 95 wt .-%, preferably 45 to 85 wt .-% and in particular 55 to 75 wt .-%, respectively based on the weight of the detergent tablets.

As part of the surfactant granules but also as an optional addition to the premix added conditioning component are builders important ingredients of Detergents and cleaners. In addition to the washing-active substances, builders are the most important ingredients of detergents and cleaners. In the invention Washing and cleaning agent moldings can all usually in washing and Be used detergents used, in particular zeolites, Silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use - even the phosphates.

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. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 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. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Crystalline, layered sodium silicates suitable as builders 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 are 2, 3 or 4. Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514 . Preferred crystalline layered silicates of the formula given are those in which M is sodium and x 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, whereby β-sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171 .

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 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 Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification 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 do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray-amorphous silicates, which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

If desired, the amount usually introduced by the surfactant granules may be used of zeolite of the P and / or X type further zeolite incorporated in the premix be added by adding zeolite as a treatment component. The used fine crystalline, synthetic and bound water-containing zeolite is preferred a zeolite of the type A, P, X or Y. However, zeolite X and mixtures are also suitable from A, X and / or P. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) on and contain preferably 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

Of course, a use of the well-known phosphates as builders possible, unless such use is avoided for environmental reasons should be. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular the tripolyphosphates.

As organic cobuilders can in the detergent tablets according to the invention 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.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, wherein among polycarboxylic acids such carboxylic acids 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 one such use is not objectionable for environmental 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 thereof.

The acids themselves can also be used. In addition to their builder action, 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 cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses 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 polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility, this can be Group again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, are preferred be.

Also suitable are copolymeric polycarboxylates, in particular 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 have proven to be suitable, the 50 to Containing 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your molecular weight, based on free acids, is generally from 2000 to 70000 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 be used. The content of the (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

To improve the solubility in water, the polymers may also be allyl sulfonic acids, such as For example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

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

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

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives, of which German Patent Application DE-A-195 40 086 discloses that they also have a bleach-stabilizing effect in addition to cobuilder properties.

Further suitable builder substances are polyacetals, which are prepared by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C 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 from Polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further 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 by conventional, for example acid or enzyme catalyzed Procedures are performed. Preferably, they are hydrolysis products with average molecular weights in the range of 400 to 500,000 g / mol. This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, where DE is a common measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100. Useful are 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 molecular weights in the range from 2000 to 30,000 g / mol.

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

Also 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. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are zeolithhaltigen and / or silicate-containing Formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present 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 co-builders are described, for example, in International Patent Application WO 95/20029 .

Another class of substances with co-builder properties are the phosphonates these are in particular hydroxyalkane or aminoalkanephosphonates. Under the hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of special importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt alkaline (pH 9). When Aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, z. B. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP, used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, be preferred to use Aminoalkanphosphonate, in particular DTPMP, or Use mixtures of the above phosphonates.

In addition, all compounds that are capable of complexes with alkaline earth ions train as co-builders.

The preparation of surfactant-containing granules is widely described in the prior art, which can be accessed in addition to extensive patent literature on numerous reviews and monographs. For example, W. Hermann de Groot, I. Adami, GF Moretti, "The Manufacture of Modern Detergent Powders", Hermann de Groot Academic Publisher, Wassenaar, 1995 describes various spray-drying, mixing and granulation processes for the production of detergents and cleaners.

For energetic reasons, it is preferred in the context of the present invention, if the surfactant-containing granules not by spray drying, but by a granulation process will be produced. In addition to conventional granulation and agglomeration processes, which are carried out in a wide variety of mixed granulators and mixed agglomerators can be used, for example, also Preßagglomerationsverfahren be used. Method, in which the surfactant-containing granules by granulation, agglomeration, press agglomeration or a combination of these methods are therefore preferred.

The granulation can be used in a variety of in the detergent industry usually used apparatus are carried out. For example, it is possible to use the common in pharmacy Verrunder. In such turntable apparatus the residence time of the granules is usually less than 20 seconds. Also conventional mixers and mixing granulators are suitable for granulation. As a mixer can be both high-intensity mixer ("high-shear mixer") and normal Mixer can be used with lower rotational speeds. Suitable mixers For example, Eirich® mixers of the R or RV series (trademarks of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixers (trademark Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (Trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim). The residence times The granules in the mixers are in the range of less than 60 seconds, with the Dwell also depends on the rotational speed of the mixer. Shorten it The residence times corresponding to, the faster the mixer is running. Preferably, the amount Residence times of the granules in the mixer / rounder under one minute, preferably below 15 seconds. In slow speed mixers, e.g. a Lödige KM, will be residence times set up to 20 minutes, with retention times under 10 minutes due to the Process economics are preferred.

In the process of press agglomeration, the surfactant-containing granules under pressure and compacted under the action of shear forces and thereby homogenized and then shaping out of the apparatus. The most technically significant pressing agglomeration processes are extrusion, roll compacting, pelleting and tableting. In the context of the present invention, preference is given to the preparation of the surfactant-containing Granules used Preßagglomerationsverfahren are the extrusion, the roll compaction and pelleting.

In order to facilitate the disintegration of highly compacted moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrating agents, 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, pp. 182-184), excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their size when water enters their volume, on the one hand increases the intrinsic volume (Swelling), on the other hand also on the release of gases pressure to be generated may cause the tablet to disintegrate into smaller particles. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic Acids can 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 washing and cleaning agent tablets contain from 0.5 to 10% by weight, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% of one or more disintegration aids, in each case based on the molding body weight.

Preferred disintegrating agents in the context of the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning agent tablets contain such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. Detergents and cleaning agent tablets containing disintegrators in granular or optionally 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 WO 98/40463 (Henkel). Further details of the production of granulated, compacted or cogranulated cellulose explosives can be found in these publications. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above-mentioned coarser disintegration aids based on cellulose 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 Rettenmaier.

Another disintegrating agent based on cellulose or as part of this component Microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack the amorphous areas (about 30% of the total cellulose mass) of the celluloses and completely dissolve, leaving the crystalline areas (about 70%) undamaged. A subsequent deaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses having primary particle sizes of about 5 microns and, for example, compactable into granules with an average particle size of 200 microns are.

Thus, in the context of the present invention, methods are preferred in which the pressing premix additionally a disintegration aid, preferably a Cellulosic disintegration aids, preferably granular, co-granulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7 Wt .-% and in particular from 4 to 6 wt .-%, each based on the weight of the premix, contains.

In further preferred methods, the premix additionally contains one or more Substances from the group of bleaching agents, bleach activators, enzymes, pH adjusters, fragrances, Perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, color transfer inhibitors and corrosion inhibitors. These substances are described below.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing 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 tablets. When cleaning or bleaching tablets for automatic dishwashing are prepared, it is also possible to use bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [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, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As bleaching agents in machine dishwashing moldings, chlorine or may also be used Bromine releasing substances are used. Among the suitable chlorine or bromine releasing materials include, for example, heterocyclic N-bromo- and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with Cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

To improve when washing or cleaning at temperatures of 60 ° C and below To achieve bleaching effect, bleach activators can be incorporated into the premix become. As bleach activators, compounds which are under perhydrolysis conditions aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, be used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups. Prefers are polyacylated 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, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place may also so-called bleach catalysts are incorporated into the moldings. For these substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing Tripod ligands as well as Co, Fe, Cu and Ru ammine complexes are used as bleach catalysts usable.

Enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof in question. Particularly suitable are from bacterial strains or Fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Preferably, subtilisin-type proteases and in particular Proteases derived from Bacillus lentus. These are enzyme mixtures, for example from protease and amylase or protease and lipase or Protease and cellulase or cellulase and lipase or protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing mixtures of special interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable. The enzymes can be adsorbed to carriers and / or embedded in encapsulants to protect against premature decomposition. Of the Proportion of enzymes, enzyme mixtures or enzyme granules in the inventive Moldings may, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 Wt .-% amount.

In addition, the detergent tablets may also contain components which have a positive effect on the oil and grease wash-out properties of textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty is already several times before with a detergent according to the invention, this oil and fat dissolving component, was washed. To the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based to the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular Polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Especially preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

The moldings can be used as optical brighteners derivatives of Diaminostilbendisulfonsäure 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 similarly constructed Compounds which, instead of the morpholino group, are a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Farther For example, brighteners of the substituted diphenylstyrene 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. Also mixtures of the aforementioned Brightener can be used.

Dyes and fragrances are the washing and Reinigungsmittelformkörpem invention added to improve the aesthetic appeal of the products and to the consumer in addition to the washing and cleaning performance a visual and sensory "typical and unmistakable "product as perfume oils or fragrances For example, individual perfume compounds, e.g. the synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and Benzylsalicylate. For example, the ethers include Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 carbon atoms, citral, Citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and Bourgeonal, to the ketones e.g. the ionone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinas. However, preference is given to using mixtures of different fragrances, which together create an appealing scent. Such perfume oils can also contain natural fragrance mixtures, as available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable Muskateller, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

Usually, the content of the detergent tablets according to the invention is Dyes below 0.01 wt .-%, while perfumes up to 2 wt .-% of the total Formulation can make.

The fragrances can be incorporated directly into the compositions according to the invention But it may also be advantageous to apply the fragrances on carriers, which the adhesion of the Enhance perfumes on the lingerie and through a slower fragrance release for long-lasting Fragrance of the textiles provide. As such carrier materials, for example Cyclodextrins proven, the cyclodextrin-perfume complexes additionally with other excipients can be coated.

To 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 the expert has no difficulty, own a high storage stability and insensitivity to the other ingredients of the Medium and against light and no pronounced substantivity to textile fibers, um do not stain them.

Prior to compression of the particulate premix to detergent tablets For example, the premix may contain finely divided surface treatment agents be "powdered". This may be for the texture and physical properties both the premix (storage, compression) and the finished detergent tablets be beneficial. Fine particulate powdering agents are in the state of Technique well known, with mostly zeolites, silicates or other inorganic salts used become. However, the premix is preferred with finely divided zeolite "powdered", wherein faujasite-type zeolites are preferred. In the context of the present Invention, the term "faujasite-type zeolite" denotes all three zeolites form the faujasite subgroup of zeolite structure group 4 (cf. Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X are therefore zeolite Y and faujasite as well Mixtures of these compounds can be used, wherein the pure zeolite X is preferred.

In the context of the present invention are methods for the preparation of washing and Preferred detergent tablets in which the or one of the admixed conditioning components a faujasite-type zeolite with particle sizes below 100 μm, preferably below 10μm and especially below 5μm and at least 0.2 Wt .-%, preferably at least 0.5 wt .-% and in particular more than 1 wt .-% of to be compressed premix makes up.

The production of the shaped body according to the invention is initially carried out by the dry Mixing the ingredients, which may be pre-granulated in whole or in part, and subsequent Informing, in particular compression to tablets, wherein conventional Method can be used. For the preparation of the invention Shaped body is the premix in a so-called template between two punches condensed into a fixed comprimat. This process, hereinafter briefly referred to as tableting is divided into four sections: dosage, compaction (elastic Deformation), plastic deformation and ejection.

First, the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting molded body by the position of the lower Stamp and the shape of the press tool can be determined. The constant dosage even at high molding throughputs is preferably a volumetric Dosing of the premix achieved. In the course of tableting the touches Upper stamp the pre-mix and lower further in the direction of the lower punch. at this compression, the particles of the premix are pressed closer to each other, wherein the void volume within the filling between the punches is continuous decreases. From a certain position of the upper punch (and thus from a certain Pressure on the premix) begins the plastic deformation, at which the particles merge and it comes to the formation of the molding. Depending on the physical Properties of the premix will also crush a portion of the premix particles and at even higher pressures sintering of the premix occurs. at increasing press speed, so high throughputs, the phase of the elastic Deformation further and further shortened, so that the resulting moldings more or may have less large cavities. In the last step of tableting, the finished moldings pushed out through the lower die from the die and through subsequent transport facilities carried away. At this time, only the Weight of the molded article finally determined because the compacts due to physical Processes (re-stretching, crystallographic effects, cooling, etc.) their shape and size can still change.

The tabletting is carried out in commercially available tablet presses, which are in principle or double stamping. In the latter case, not only the upper punch used for pressure build-up, also the lower punch moves during the Pressing on the upper punch, while the upper punch presses down. For small production quantities are preferably used in eccentric tablet presses the one or more stamps are attached to an eccentric disc, which in turn to a Axis is mounted at a certain rotational speed. The movement of this Preßstempel is similar to the operation of a conventional four-stroke engine. The compression can be done with a top and bottom stamp, but it can also be several Stamp be attached to an eccentric disc, the number of die holes is extended accordingly. The throughputs of eccentric presses vary according to type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs you can choose rotary tablet presses, where on a so-called Matrizentisch a larger number of matrices is arranged in a circle. The Number of matrices varies depending on the model between 6 and 55, with larger matrices are commercially available. Each die on the die table is a top and bottom stamp assigned, in turn, the pressing pressure active only by the upper or lower punch, but can also be built by both stamps. The die table and the Stamps move around a common perpendicular axis, with the stamp by means of rail-like cam tracks during circulation in the positions for filling, Compression, plastic deformation and ejection are brought. In the places where a particularly serious increase or decrease of the stamp required is (filling, compaction, ejection), these curved paths are supplemented by Low pressure pieces, Nierderzugschienen and Aushebebahnen supported. The filling the die is made via a rigidly arranged supply device, the so-called Fill shoe connected to a pre-mix reservoir. The pressing pressure the pre-mix can be individually adjusted via the pressing paths for upper and lower punches, wherein the pressure build-up by the rolling forward of the punch shaft heads on adjustable Pressure rollers happens.

Concentric presses can also be equipped with two filling shoes to increase throughput be, with the preparation of a tablet only a semicircle are passed through got to. To produce two-layered and multi-layered shaped bodies, several filling shoes are used arranged one behind the other without the slightly pressed first layer before further filling is ejected. By suitable process control are in this way also shell and point tablets produced, which have a onion-bowl-like structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible. Rotary tablet presses are also available Can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing. The throughputs of modern rotary tablet presses amount to 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 tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. Small variations 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
• Tuning of the filling paddle speed to the speed of the rotor
• Filling shoe with constant powder height
• Decoupling of filling shoe and powder template

To reduce Stempelanbackungen offer all known from the art Non-stick coatings on. Particularly advantageous are plastic coatings, Plastic inserts or plastic stamps. Even rotating stamps have proven to be beneficial proven, where possible upper and lower punch be made rotatable should. With rotating punches can be dispensed with a plastic insert usually become. Here, the stamp surfaces should be electropolished.

It has also been shown that long pressing times are advantageous. These can be with pressure rails, several pressure rollers or low rotor speeds are set. Because the Hardness fluctuations of the tablet caused by the fluctuations of the pressing forces, Systems should be used which limit the pressing force. Here can be elastic Used punches, pneumatic compensators or resilient elements in the force path become. Also, the pressure roller can be made resilient.

Tableting machines suitable for the purposes of the present invention are, for example available from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Berne (CH) and Courtoy N.V., Halle (BE / LU). For example, the hydraulic double pressure press HPF is particularly suitable 630 of the company LAEIS, D.

The moldings can be made in a predetermined spatial form and predetermined size become. As a form of space come practically all useful manageable configurations considered, for example, the training as a blackboard, the bar or bar form, Cube, cuboid and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross-section. This last embodiment detects the presentation form of the tablet to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each as separate individual elements be formed, the predetermined dosage of the detergent and / or detergent equivalent. However, it is also possible to form compacts, a plurality connect such mass units in a compact, in particular by predetermined Predetermined breaking points the easy separability of portioned smaller units provided is. For the use of textile detergents in machines of the type common in Europe with horizontally arranged mechanism, the formation of the portioned compacts as Tablets to be useful in cylindrical or cuboidal shape, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, Eccentric or rotary presses are suitable devices in particular for producing such compacts.

The spatial form of another embodiment of the moldings is in their dimensions the Einspülkammer adapted from commercial household washing machines, so that the Moldings can be metered without dosing directly into the dispenser, where it dissolves during the flushing process. Of course, but also an assignment the detergent molding via a dosing easily possible and in the context of present invention.

Another preferred molded article which can be produced has a plate or panel-like structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin ones Segments, aborted and entered into the machine. This Principle of the "bar-shaped" molding detergent can also be used in other geometric Shapes, such as vertical triangles, only on one side alongside each other, be realized.

It is also possible, however, that the various components are not uniform Tablet are pressed, but that moldings are obtained, the several layers, So at least two layers. It is also possible that these different Layers have different dissolution rates. From this you can advantageous performance properties of the molded articles result. For example Components contained in the moldings are mutually negative it is possible to influence the one component in the faster soluble layer integrate and incorporate the other component into a slower soluble layer, so that the first component has already reacted when the second goes into solution. The layer structure of the moldings can be carried out either in a stack, wherein a solution process the inner layer (s) already takes place at the edges of the shaped body, if the outer layers are not yet completely dissolved, but it can also be a complete encasement of the inner layer (s) by the further outer layer (s) Layer (s) are achieved, resulting in a prevention of premature solution of components the inner layer (s) leads.

In a further preferred embodiment of the invention, a shaped body is made at least three layers, so two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach while in the stack-shaped molded body, the two outer layers and the shell-shaped Shaped body, however, the outermost layers are free from peroxy bleach. Furthermore is it is also possible to use peroxy bleach and any bleach activators present and / or to spatially separate enzymes in a molding. such multilayer molded bodies have the advantage that they not only have a Einspülkammer or via a metering device, which is added to the wash liquor, can be used; Rather, it is also possible in such skins, the molding in the to give direct contact to the textiles in the machine, without any stains Bleaching agents and the like would be feared.

Similar effects can also be achieved by coating ("coating") individual constituents of the to be pressed detergent composition or the whole Obtain molding. For this purpose, the bodies to be coated can be used, for example aqueous solutions or emulsions, or via the process of Schmelzbesehichtung receive a coating.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable σ = 2 P π dt

Herein, σ stands for the diametrical fracture stress (DFS) in Pa, P is the force in N that leads to the pressure exerted on the molding that breaks it D is the shape diameter in meters and t is the height of the molding Moldings.

Another object of the present invention is the use of cooled Premixes with temperatures below 15 ° C for the production of detergents and cleaners supply medium molded bodies. This use according to the invention of the cooled premixes leads to moldings with advantageous properties, such as the examples below demonstrate. With regard to preferred embodiments of the use according to the invention (lower temperatures, composition of the premix, etc.) is analogous to the above What has been said for the method according to the invention.

Examples:

By wet granulation in a 130-liter ploughshare mixer the company Lödige was one Surfactant granules prepared, whose composition is given in Table 1. In connection The granules were granulated in an Aeromatic fluidized bed apparatus dried at an inlet temperature of 60 ° C for 30 minutes. After drying was the granules are sieved to remove the fines <0.4 mm and coarse particles> 1.6 mm.

The surfactant granules were then treated with further components to form a compressible premix, the composition of which is given in Table 2. The compressible premix was cut in half and each half packed airtight. The two subsets of the premix were stored for 18 h at different temperatures (according to the invention: 9 ° C, Comparative Example: room temperature, 22 ° C) and then unpacked and in a Korsch eccentric press to tablets (diameter: 44 mm, height: 22 mm, weight : 37.5 g) pressed. The measured values of the tablet hardness and decay times are in each case the mean values of a double determination, the individual values for each type of molded article varying by a maximum of 2 N or 2 s. Table 2, which shows the composition of the premixes, also indicates the temperature of the respective premix immediately before the pressing operation. Composition of the surfactant granules [% by weight] C _9-13 alkyl benzene sulphonate 19.4 C _12-18 fatty alcohol sulfate 5.2 C _12-18 fatty alcohol with 7 EO 4.8 Soap 1.6 C _12-16 fatty alcohol 1,4-glucoside 1.0 sodium 17.0 Zeolite A 28.5 sodium silicate 5.6 Na-hydroxyethane-1,1-diphosphonate 0.8 Acrylic acid-maleic acid copolymer 5.6 optical brightener 0.3 Water, salts rest Composition of premixes [% by weight]: e V Surfactant granules (Table 1) 62.9 62.9 sodium 17.0 17.0 TAED 7.3 7.3 foam inhibitor 3.5 3.5 enzymes 1.7 1.7 Repel-O-Tex® SRP 4 1.1 1.1 Perfume 0.5 0.5 Wessalith® P (zeolite A) 1.0 1.0 Disintegration Aid (Cellulose) 5 5 Temperature of premix before compression [° C] 9.8 21.4

The hardness of the tablets was after preparation by deformation of the tablet until measured to break, with the force acting on the side surfaces of the tablet and the maximum strength that withstood the tablet was detected.

To determine the tablet disintegration, the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C) and measured the time to complete tablet disintegration. The experimental data are shown in Table 3: Detergent tablets [physical data] tablet e V Tablet hardness [N] 40 39 Decay time [s] 9 11 Tablet hardness [N] 49 52 Decay time [s] 13 24 Tablet hardness [N] 58 61 Decay time [s] 28 48

Table 3 shows that the disintegration times of detergent tablets by the procedure according to the invention can be significantly reduced, which is especially true in higher hardness results in significant improvements.

Claims (11)

1. Process for producing laundry detergent and cleaning composition tablets by compressive shaping in a manner known per se, characterized in that the premixture to be compressed has a temperature below 15°C immediately before the compression.
2. Process according to Claim 1, characterized in that the premixture to be compressed has a temperature below 13°C und in particular below 10°C immediately before the compression.
3. Process according to either of Claims 1 or 2, characterized in that the premixture to be compressed comprises surfactant-containing granule(s) and further formulation components.
4. Process according to Claim 3, characterized in that the premixture to be compressed comprises a surfactant-containing granule which comprises anionic and/or nonionic surfactants and builders, and whose total surfactant content is 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight, based in each case on the surfactant granule.
5. Process according to either of Claims 3 or 4, characterized in that the surfactant-containing granule has particle sizes between 100 and 2000 µm, preferably between 200 and 1800 µm, more preferably between 400 and 1600 µm and in particular between 600 and 1400 µm.
6. Process according to any of Claims 3 to 5, characterized in that the fraction of the surfactant-containing granule in the laundry detergent and cleaning composition tablets is 40% to 95% by weight, preferably 45 to 85% by weight and in particular 55 to 75% by weight, based in each case on the weight of the laundry detergent and cleaning composition tablets.
7. Process according to any of Claims 1 to 6, characterized in that the premixture to be compressed has a bulk density of at least 500 g/l, preferably at least 600 g/l and in particular about 700 g/l.
8. Process according to any of Claims 1 to 7, characterized in that the premixture to be compressed additionally comprises a disintegration assistant, preferably a cellulose-based disintectration assistant, preferably in granular, co-granulated or compacted form, in amounts of 0.5 to 10% by weight, preferably of 3 to 7% by weight and in particular of 4 to 6% by weight, based in each case on the weight of the premixture.
9. Process according to any of Claims 3 to 8, characterized in that the or one of the formulation components added is a zeolite of the faujasite type having particle sizes below 100 µm, preferably below 10 µm and in particular below 5 µm, and make up at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight, of the premixture to be compressed.
10. Process according to any of Claims 1 to 9, characterized in that the premixture to be compressed further comprises one or more substances from the group of the bleaches, bleach activators, enzymes, pH modifiers, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, greying inhibitors, dye transfer inhibitors and corrosion inhibitors.
11. Use of cooled premixtures having temperatures below 15°C for producing laundry detergent and cleaning composition tablets.