EP0863200A2 - Detergent compositions in tablet form - Google Patents

Abstract

Production of a detergent bodies (e.g. tablets) containing surfactants, builders, etc. is by pressing a particulate composition comprising (by wt., based on total body) : (A) 5-20% super-dried amorphous silicate; (B) 0.5-10% polyethylene glycol; and (C) 1-15% water or an aqueous solution. Preferably (A) is amorphous silicate with delayed disintegration and (B) has mol wt. 4,000 (i.e. is PEG 4000) and is used especially at 1-4%, while (C) is especially used at 3-8%. Optionally also present as additional builders are oligo- and/or polymeric polycarboxylates (especially citrates) and/or acrylic acid/maleic acid copolymers. The total surfactant content is 5-60 (especially above 15) wt.%, with a greater amount of anionic than nonionic surfactant being used and the nonionic surfactants being alkyl polyglycosides.

Description

The present invention is in the field of compressed washing and cleaning agents. It comprises a process for the production of detergent tablets, with advantageous product properties such as hardness, breaking strength and good solubility with process advantages such as low equipment costs, low Pressing forces and low temperatures can be combined.

Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents have a number of advantages over powdered detergents: you are easier to dose and handle and because of their compact size Structure advantages in storage and transportation. Also in the patent literature Detergent tablets thus described comprehensively.

For example, EP-A-0 522 766 (Unilever) discloses shaped bodies made of a compact, particulate Detergent composition, wherein at least part of the particles with a material that is coated both as a binder and as a disintegrant acts when dissolving the moldings in water. This document also refers to the general Difficulty, molded body with adequate stability and good solubility to manufacture. The particle size in the mixture to be compressed should be above of 200 µm, the upper and lower limits of the individual particle sizes not should deviate from each other by more than 700 µm.

Other publications that deal with the production of detergent tablets, are EP-A-0 716 144 (Unilever), the moldings with an external shell made of water-soluble Material describes, as well as EP-A-0 711 827 (Unilever), the ingredient contain a citrate with a defined solubility.

The use of binders, in particular polyethylene glycol, is described in EP-A-0 711 828 (Unilever), which describes detergent tablets which are formed by pressing a particulate detergent composition at temperatures between 28 ° C and the melting point of the binding material, always below the melting temperature is pressed. From the examples in this document it can be seen that that the moldings produced according to their teaching higher breaking strengths have when pressing at elevated temperature.

Sintern

weiter erhöht werden soll.All of the cited documents use high pressures above 15 N / cm ² in the pressing process in order to obtain sufficiently stable molded articles. If necessary, the pressing operations are additionally carried out at elevated temperature, the stability being determined by a kind

Sintering

should be increased further.

The object of the present invention was to provide a simplified method of manufacture to provide moldings, the moldings with regard to their breaking strength, Storage stability and their dissolution behavior exceed the known moldings.

a) 5 bis 20 Gew.-% eines übertrockneten amorphen Silikats,

b) 0,5 bis 10 Gew.-% Polyethylenglycol und

c) 1 bis 15 Gew.-% Wasser oder wäßrige Lösungen,

jeweils bezogen auf das Gewicht des entstehenden Formkörpers, eingesetzt werden.The invention accordingly relates to a process for the production of detergent tablets, comprising surfactants, builders and optionally further detergent constituents, by pressing a particulate detergent composition, for the preparation of the tablets

a) 5 to 20% by weight of an over-dried amorphous silicate,

b) 0.5 to 10 wt .-% polyethylene glycol and

c) 1 to 15% by weight of water or aqueous solutions,

each based on the weight of the resulting molded body, are used.

To produce the detergent tablets, a powdery or granular, free-flowing premix is pressed in suitable forms in the process according to the invention. The pressing can take place at any temperature and any pressing pressure. While usually only high compression pressures and / or temperatures lead to sufficiently stable moldings, detergent tablets can be produced by the process according to the invention which, with compression pressures below 15 N / cm ² , already outperform the conventional moldings in terms of stability. Working at an elevated temperature can also be dispensed with in the method according to the invention, although working at a higher temperature can be useful and does not lead to the loss of the advantages of the method according to the invention. Usually, an increase in temperature at the same pressing pressure leads to a higher breaking strength of the moldings. At the same time with reduced pressure and elevated temperature, moldings are obtained which, despite their high breaking strength, have a good dissolution rate. However, the process according to the invention is preferably carried out with compression pressures below 15 N / cm ² and at temperatures below 30 ° C., which leads to moldings which, in terms of their stability and dissolving values, outperform conventional detergent tablets. The low pressing temperatures are particularly advantageous when the moldings contain temperature-labile ingredients that would tend to decompose at elevated temperatures.

The particulate detergent and cleaning agent composition, which is pressed into the molded article, contains 5 to 20% by weight of an over-dried amorphous silicate, 0.5 to 10% by weight of polyethylene glycol and 1 to 15% by weight of water or aqueous solutions of others Active ingredients and auxiliaries. As a result of this special composition, laundry detergent and cleaning product tablets are obtained even at low compression pressures and without the use of elevated temperatures, which combine high stability with excellent dissolving properties. The particulate detergent and cleaning agent composition, which is pressed into the shaped body, can be produced in any known manner and can in principle have any bulk density. Parts of the composition or even the complete composition can thus be produced by the process of spray drying or roller compaction. However, the particulate detergent and cleaning agent composition is produced with particular advantage by granulating and compressing its ingredients or individual compounds in mixing granulators. The granulation can be carried out in both high-intensity and slow-running mixers. Examples of high-speed mixers are the Lödige® CB 30 recycler (trademark of Lödige Maschinenbau GmbH, Paderborn), the Fukae® FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Japan), the Eirich® mixer type R ( Trademarks of the machine factory Gustav Eirich, Hardheim) or the Drais® K-TTP 80 (trademark of Drais-Werke GmbH, Mannheim), examples of slow-speed mixing granulators are the Drais® KT 160 and the Lödige® KM 300. The latter, which is often called Lödige ploughshare mixers is particularly suitable for carrying out this process step.

In a particularly preferred embodiment, the production of mixed granulation is carried out of the premix to be pressed, the over-dried amorphous silicate in the mixer submitted, further optional builder components and auxiliary substances added and with the mixer running, water or aqueous solutions added, followed by the surfactants or surfactant compounds are added. In the preparation stage the other detergent and cleaning agent components such as bleach, Enzymes, soil repellents and the like are added. The one used as component b) Polyethylene glycol can be used together with the surfactant compounds in the first step or else with the remaining ingredients are added in the preparation step. Prefers is the addition in the preparation step. The polyethylene glycol can be commercially available Forms are added, the melting points depending on the molecular weight distribution vary. Polyethylene glycol with an average molecular weight of 1500 Dalton (PEG 1500) melts at 45 ° C, for example, with a molecular weight of 4000 Dalton (PEG 4000) or 6000 Dalton (PEG 6000) melts at approx. 55 ° C or 62 ° C. PEG 4000 is preferred in amounts between 0.5 to 10% by weight, preferably from 1 to 4 % By weight, based on the weight of the shaped body, is used. Can continue with the manufacture the molded body can also be used organic polymeric substances which in Combination with the polyethylene glycol contributes to the strength of the molded articles. For example, polyvinyl pyrrolidone, polyacrylates and copolymers are made here Maleic acid and acrylic acid called.

The bulk density of the premix to be compressed can vary within wide limits, depending on the density of the molded bodies that are to be formed. For reasons in the packaging and transport economy, bulk weights of the premix are above Aim for 400 g / l, with higher bulk weights, in particular over 500 g / l and more than 600 g / l are particularly preferred. Such bulk densities lead to molded body densities above 800 g / l, which in turn for reasons of packaging and The aim is to achieve transportation economics.

The granules or the granulate mixtures are usually compressed at Room temperature or at best slightly elevated temperatures, for example in Temperature range up to about 50 ° C. Preference is given to pressing in the room temperature range, So made in the range of about 18 to 30 ° C. The duration of the pressing process is determined by the machine type selected. It is in usually less than 1 minute and is usually in the range of a few seconds or significantly below.

The portioned compacts can have a predetermined spatial shape and a predetermined size are manufactured.

Practically all usable configurations come into consideration as spatial form, for example, the training as a board, the shape of bars or bars, cubes, Cuboid and corresponding room elements with flat side surfaces and in particular cylindrical configurations with 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 separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents corresponds. However, it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by predetermined breaking points make it easy to separate portioned smaller units is provided. For the use of laundry detergents in machines common in Europe Type with horizontally arranged mechanics can be the formation of the portiorated Compacts as tablets, in the shape of a cylinder or cuboid, are expedient, one Diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial Hydraulic presses, eccentric presses or rotary presses are suitable Devices in particular for the production of such compacts.

The spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction bowl without a metering aid, where they are dissolves during the induction process. It goes without saying that the Detergent tablets easily possible via a dosing aid and within the scope of present invention preferred.

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

But it is also possible that the various components do not become one Tablet are pressed, but that shaped bodies are obtained which have several layers, thus have at least two layers. It is also possible that these different Layers have different dissolving speeds. From this you can advantageous application properties of the molded articles result. If For example, components are contained in the moldings, which are mutually reciprocal affect negatively, so it is possible that one component is more soluble in the Integrate layer and the other component into a slower soluble layer incorporate so that the first component has already reacted when the second in solution goes. The layer structure of the moldings can be stacked, a dissolution process of the inner layer (s) at the edges of the molded body already then occurs when the outer layers are not yet completely dissolved, it can but also a complete covering of the inner layer (s) by the further external layer (s) can be reached, which prevents the early Solution of components of the inner layer (s) leads.

In a further preferred embodiment of the invention, a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Shaped bodies, however, the outermost layers are free of peroxy bleach. Farther it is also possible to use peroxy bleach and any bleach activators present and / or to separate enzymes spatially from one another in a shaped body. Such Multi-layer moldings have the advantage that they do not have only one induction chamber or via a dosing device which is added to the wash liquor, can be used; rather, it is also possible in such cases, the molded body into the machine in direct contact with the textiles without staining would be feared by bleach and the like.

Similar effects can also be achieved by coating ( coating ) individual components of the detergent composition to be pressed or the entire molded body. 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 method of melt coating.

The silicates used according to the invention are over-dried amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably of 1: 2 to 1: 2.8 and in particular of 1: 2 to 1: 2, 6, which have water contents below 15% by weight, based on the weight of the silicate. Conventional amorphous silicates, so-called glasses of water have residual water contents between 17 and 20 wt .-%, so that the term overdry in the context of this application means that the water content of the silicate used is below 15% by weight. Overdried amorphous silicates which are delayed in dissolution and have secondary washing properties are to be used with preference in the process according to the invention. The delayed disintegration compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting / compression or by drying alone. In the context of this invention, the term “amorphous” also means “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas ranging in size from 10 to a few hundred μm, 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 also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 (Henkel). The silicate compounds can, for example, also contain other builder substances in amounts below 10% by weight. Silicate / soda / nonionic surfactant compounds are used with particular advantage in the process according to the invention.

The water introduced into the process according to the invention is used in the production of the Premix to be pressed (the particulate detergent and cleaning agent composition) applied to the silicate particles. This can either be pure Water are added, or an aqueous solution of active ingredients and auxiliary substances, which are usually used in detergents and cleaning agents. The water or the aqueous solutions are used in amounts of 1 to 15% by weight, based on the weight the shaped body, added during granulation, quantities are particularly preferred from 2 to 10, in particular from 3 to 8% by weight, based on the weight of the shaped body. Pure water is preferably added, which contains no solutes.

If the process according to the invention is carried out using an over-dried amorphous silicate, Polyethylene glycol and water carried out, so you get stable tablets that additionally harden after storage. If the water is not added separately, but from the outset, a silicate with a higher water content is used to create otherwise the same procedure (compression pressure, time, temperature) unstable tablets do not harden after storage and have extremely low breaking strength. Of the Use of over-dried water glasses with water contents below 15% by weight and the addition of water are essential for the success of the method according to the invention.

In the particulate detergent and cleaning agent composition to be pressed can use anionic, nonionic, cationic and / or amphoteric surfactants will. From an application point of view, mixtures of anionic are preferred and rich ionic surfactants, the proportion of anionic surfactants should be greater than the proportion of nonionic surfactants. The total surfactant content of the moldings is at 5 to 60% by weight, based on the weight of the shaped body, with surfactant contents above 15 % By weight are preferred.

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

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

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C _12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C _10-20 oxo alcohols and those half esters 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. C _16-18 alk (en) yl sulfates are particularly preferred for reasons of washing technology. It can also be particularly advantageous and particularly advantageous for machine washing agents to use C _16-18 alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and at relatively low washing temperatures from, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably C _12-18 fatty alkyl sulfates or mixtures of C _12-14 fatty alkyl sulfates or C _12-18 fatty alkyl sulfates with C _16-18 fatty alkyl sulfates and in particular C _12-16 fatty alkyl sulfates with C _16-18 fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C ₁₆ to C ₂₂ are used. Mixtures of saturated sulfated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol® type (commercial product of the applicant). Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred. 2,3-Alkyl sulfates, which can be prepared, for example, by addition of sulfuric acid onto α-olefins, are also suitable.

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

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

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

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533 will.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially 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 Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

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

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

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, 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 overdried amorphous silicates used according to the invention, other builder and cobuilder substances can also be used in the detergent compositions. These include in particular zeolites, citrates and polymeric polycarboxylates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP ^(R) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use is not avoided for ecological reasons should be. The sodium salts of the orthophosphates are particularly suitable, the pyrophosphates and especially the tripolyphosphates. Their salary is generally not more than 25% by weight, preferably not more than 20% by weight, in each case on the finished product. In some cases it has been shown that tripolyphosphates in particular even in small quantities up to a maximum of 10% by weight, based on the finished product Medium, in combination with other builder substances for a synergistic improvement of secondary washing power.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 from these.

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 value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. 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 for is the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups 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 can be used. A preferred dextrin is described in British patent application 94 19 091. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Are particularly preferred in this context also glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat U.S. Patents US 4,524,009, US 4,639,325, in European Patent application EP-A-0 150 930 and Japanese patent application JP 93/339896 to be discribed. Suitable amounts are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which have at least 4 carbon atoms and at least one hydroxy group as well contain a maximum of two acid groups. Such cobuilders are used, for example, in the international patent application WO-A-95/20029.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight from 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. Copolymers of Acrylic acid with maleic acid, 50 to 90 wt .-% acrylic acid and 50 to 10 % By weight of maleic acid. Their relative molecular mass, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000, and especially 50000 to 100000.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00 772, are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Other suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as, for example are described in international patent application WO-A-93/08251 or their Manufactured, for example, in international patent application WO-A-93/16110 is described. Oxidized oligosaccharides according to the older ones are also suitable German patent application P 196 00 018.1.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives, of which in the German patent application P 195 40 086.0 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example, as in European patent application EP-A-0 280 223 can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

In addition to the ingredients mentioned, the detergent tablets can known additives commonly used in detergents, for example Bleaching agents and bleach activators, foam inhibitors, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, Contain opacifiers or pearlescent agents.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 1 to 40% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.

To improve the bleaching effect when washing at temperatures of 60 ° C and below to achieve this, bleach activators can be incorporated into the preparations. As Bleach activators can be compounds that are aliphatic under perhydrolysis conditions Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Are preferred multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well as acetylated sorbitol and mannitol or their in the European Patent application EP 0 525 239 mixtures described (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaaceryl lactose as well as acetylated, optionally N-alkylated glucamine and Gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The from the German patent application DE 196 16 769 known hydrophilically substituted acylacetals and in German patent application DE 196 16 770 and international patent application Acyl lactams described in WO 95/14075 are also preferably used. The combinations known from German patent application DE 44 43 177 conventional bleach activators can be used. Such bleach activators are in the usual range of amounts, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.

In addition to the conventional bleach activators listed above or other The place from the European patents EP 0 446 982 and EP 0 453 003 known sulfonimines and / or bleach-enhancing transition metal salts or contain transition metal complexes as so-called bleaching catalysts be. The transition metal compounds in question include in particular known from the German patent application DE 195 29 905 manganese, iron, Cobalt, ruthenium or molybdenum salt complexes and those from the German patent application DE 196 20 267 known N-analog compounds, which from the German Patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or Molybdenum-carbonyl complexes, which are described in German patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogenous tripod ligands resulting from the German patent application DE 196 20 411 known cobalt, iron, copper and ruthenium amine complexes, those described in German patent application DE 44 16 438 Manganese, copper and cobalt complexes described in the European patent application Cobalt complexes described in EP 0 272 030, which result from the European patent application EP 0 693 550 known manganese complexes, which from the European patent EP 0 392 592 known manganese, iron, cobalt and copper complexes and / or those in European patent specification EP 0 443 651 or European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and Manganese complexes described in EP 0 544 519. Combinations of bleach activators and transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 and international patent application WO 95/27775 known. Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are used in conventional amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on all means.

In addition, the agents can also contain components that make oil and fat washable made of textiles. This effect is particularly evident if a textile is soiled, which has previously been repeatedly with an inventive Detergent containing this oil and fat-dissolving component is washed has been. The preferred oil and fat dissolving components include, for example non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, as well as the polymers of phthalic acid and / or of the known from the prior art Terephthalic acid or its derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. Of these, the sulfonated ones are particularly preferred Derivatives of phthalic acid and terephthalic acid polymers.

According to the teaching of international patent application WO-A-94/01222, alkali carbonates also by sulfur-free, 2 to 11 carbon atoms and optionally one further carboxyl and / or amino groups and / or amino acids Salts to be replaced. In the context of this invention, it is possible that a partial until the alkali carbonates are completely replaced by glycine or glycinate.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

The salts of polyphosphonic acids are preferably the neutral sodium salts for example 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylene diamine tetramethylene phosphonate in amounts from 0.1 to 1.5% by weight.

Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, amylase and Lipase or protease, lipase and cellulase, but especially mixtures containing cellulase of special interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to prevent them from premature decomposition protect. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The moldings can be derivatives of diaminostilbenedisulfonic acid as optical brighteners 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 a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also 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) diphenyl. Mixtures of the aforementioned Brighteners can be used.

After pressing, the laundry detergent and cleaning product tablets have an initial stability which increases over time due to post-curing. Post-curing times of several days are usually to be observed, whereby the breaking strength can increase by a factor of 2 to 3. Detergent tablets produced by the process according to the invention have high breaking strengths shortly after production, which increases to about 90 percent of their final value in the course of 2 hours. A further increase in the breaking strength during storage is not observed. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to

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

The dissolving rate or the residue behavior of the shaped bodies can be determined using several test methods. To measure the rate of disintegration, a shaped body was added to 3.5 kg of dry laundry in a washing machine (Miele Novotronic W 918) in a conventional metering device. After water had run in, the metering device was weighed with the shaped body. A colored wash program (40 ° C, 11 l water, 16 ° d) was then carried out. After 5 and 10 minutes, the washing program was interrupted and the metering device with the remains of the shaped body was weighed. The residue in% by weight of the initial value is given as the test result.
To determine the rate of decay in units of time, an online washing machine (Miele Deluxe W 717) equipped with a conductivity measuring cell was loaded with 4.5 kg of filling laundry and a washing program (40 ° C., 17 l of water, 16 ° d) was started after the addition of a shaped body. The time until the conductivity is constant corresponds to the time required for the molded article to dissolve completely.

Examples

By molding a particulate premix (for composition, see Table 1), the moldings E1 to E5 were obtained, which are characterized by the physical data given in Table 2. The comparative examples V1 to V5 in Table 2 are taken from the patent literature. The comparative examples S1 and S2 correspond in their composition to example E3 according to the invention, except that in each case the over-dried amorphous silicate was mixed with a water glass normal Water content of 18 wt .-% replaced and the amount of free water added reduced accordingly. Composition [% by weight] E1 E2 E3 E4 E5 Alkyl polyglycoside 3.34 3.34 7.56 3.31 4.13 C _12-14 fatty alcohol sulfate 3.85 3.86 - 3.77 5.21 C _12-18 fatty alcohol sulfate 15.39 15.42 - 15.07 12.32 C _12-18 tallow alcohol sulfate - - 14.07 - - Sodium sulfate 5.13 5.14 - 5.02 4.21 Sodium citrate 14.30 18.24 11.97 14.01 16.20 Sokalan-CP5® 4.33 4.32 5.40 4.25 4.20 Phosphonate 0.41 0.41 0.53 0.51 0.40 Water glass 11.67 9.08 18.15 11.46 12.71 should repellent 0.97 1.00 1.00 0.95 0.97 Foam inhibitor 3.45 3.50 3.50 3.38 3.38 Protease 1.53 1.50 1.56 1.51 1.50 Tylose 0.26 0.24 0.48 0.46 0.25 opt. Brightener 0.13 0.13 0.14 0.13 0.15 Sodium percarbonate 17.76 17.00 17.50 17.40 16.50 TAED 7.13 7.13 7.25 7.00 6.24 Perfume 0.26 0.30 0.25 0.25 0.20   PEG 4000 2.05 2.00 2.00 3.98 6.22 otherwise. salts 1.05 1.07 0.98 1.47 0.87 water 6.99 6.33 7.66 6.07 4.34 Total surfactant content 22.58 22.62 21.63 22.15 21.66 Sokalan CP5® is an acrylic acid-maleic acid copolymer from BASF physical data of the moldings [units: see table] E1 E2 E3 E4 E5 V1 V2 V3 V4 V5 Molded body height [cm] 2nd 2nd 2.7 2.3 2.4 1 2.5 2.5 2nd 2nd Shaped body ⊘ [cm] 4.4 4.4 5 5 5 4th 4.5 4.5 4.5 4.5 Molded body weight [g] 25th 25th 40 40 40 ng ng ng 50 50 Density [g / cm ³ ] 0.82 0.82 0.75 0.89 0.85 ng 1.24 1.39 1.25 1.40 Pressing force [kN] <10 <10 0.2 0.2 0.2 0.126 0.9 3.3 1.1 2.8 Pressure [N / cm ² ] <6.6 <6.6 10.2 10.2 10.2 10.0 56.6 207 69.2 176 Breaking strength [kPa] 44.9 35.4 28.3 67.0 57.8 28.6 7.5 19th 4.5 15 Residue [% by weight] 0 0 0 0 0 0 0 70 0 85 Dissolution time [min] 8th 5 5 3.5 4.5 ng ng ng ng ng ng: not mentioned
V1: Detergent tablets with individually coated components of a defined size, coating made of polymer (branched polyvinylpyrrolidone)
produced according to the teaching of EP-A-0 522 766
V2, V3: Detergent tablets containing a sodium citrate of certain solubility
produced according to the teaching of EP-A-0 711 827
V4, V5: Detergent tablets containing 4.8% by weight of PEG 4000 as a binder, produced according to the teaching of EP-A-0 711 828

Instead of the over-dried amorphous silicate ( over-dried water glass ) If a not over-dried water glass with a water content of 18% by weight is used with a correspondingly reduced addition of water (comparative examples S1 and S2), the mixture does not give any tablets at pressing forces of 200 N, which means that when it is ejected from the press it occurs as a result from instability to tablet destruction (S1). Stable tablets could only be obtained with compressive forces of 25 kN (S2). These tablets are characterized by poor solubility and high residue formation. physical data of the moldings [units: see table] E1 E2 E3 E4 E5 S1 S2 Molded body height [cm] 2nd 2nd 2.7 2.3 2.4 2.7 2.7 Shaped body ⊘ [cm] 4.4 4.4 5 5 5 5 5 Molded body weight [g] 25th 25th 40 40 40 40 40 Density [g / cm ³ ] 0.82 0.82 0.75 0.89 0.85 0.75 0.88 Pressing force [kN] <10 <10 0.2 0.2 0.2 0.2 25th Pressure [N / cm ² ] <6.6 <6.6 10.2 10.2 10.2 10.2 1273 Breaking strength [kPa] 44.9 35.4 28.3 67.0 57.8 30th Residue [% by weight] 0 0 0 0 0 - 20th Dissolution time [min] 8th 5 5 3.5 4.5 - 17th

Claims (9)

Process for the production of detergent tablets, containing surfactants, builders and optionally further detergent components, by pressing a particulate detergent composition, characterized in that for the production of the tablets a) 5 to 20% by weight of an over-dried amorphous silicate, b) 0.5 to 10 wt .-% polyethylene glycol and c) 1 to 15% by weight of water or aqueous solutions, each based on the weight of the resulting molded body, are used. A method according to claim 1, characterized in that the particulate detergent composition is pressed at temperatures below 30 ° C and pressing forces below 15 N / cm ² . Method according to one of claims 1 to 2, characterized in that as a component a) amorphous silicates with delayed disintegration are used. Method according to one of claims 1 to 3, characterized in that a polyethylene glycol with the average molecular weight 4000 (PEG 4000) in quantities from 0.5 to 10, preferably from 1 to 4 wt .-%, is used. Method according to one of claims 1 to 4, characterized in that 3 to 8 % By weight of water or aqueous solutions can be used. Method according to one of claims 1 to 5, characterized in that as further Builder substances, oligomeric and / or polymeric polycarboxylates, in particular Citrates and / or acrylic acid-maleic acid copolymers are used. Method according to one of claims 1 to 6, characterized in that the total surfactant content the shaped body 5 to 60% by weight, preferably more than 15% by weight, based on the weight of the molded body. Method according to one of claims 1 to 7, characterized in that as surfactants nonionic and anionic surfactants are used, the proportion of anionic surfactants is greater than the proportion of nonionic surfactants. Method according to one of claims 1 to 8, characterized in that as non-ionic Alkyl polyglycoside (APG) surfactants are used.