DE19851426A1 - Producing multiphase, shaped detergents or washing agents by covering shaped premix with melt-emulsion or -suspension of covering material containing dispersed active materials such as bleaches to give controlled release in use - Google Patents

Abstract

Producing multiphase, shaped detergents or washing agents comprises covering shaped premix with melt-emulsion or -suspension of covering material containing dispersed active materials such as bleaches to give controlled release in use. Production of a multiphase, shaped detergent or washing agent comprises: pressing a particulate pre-mix to form a shape with a hollow, preparing a melt-suspension or -emulsion containing a covering material of melting point above 30 deg C having active material(s) dispersed in it; filling the shape with the composition prepared in (ii) at above the melting point of the covering material; and cooling and optionally post-treating the agent.

Description

The present invention is in the field of manufacturing washing and cleaning stocks ver molded body. In particular, it relates to processes for the production of multi-phase washing and detergent tablets, in which the division into several phases parts are achieved in the washing and cleaning activity. Such washing and cleaning Detergent tablets comprise, for example, detergent tablets for washing of textiles, detergent tablets for machine dishwashing or Cleaning hard surfaces, bleach tablets for use in washing or cleaning dishwashers, water softening tablets or stain remover tablets.

Detergent tablets of the named product classes are in the prior art Technology is widely described and is popular with consumers because of the simple dosage increasing popularity. Tableted detergents and cleaning agents have opposite Powdery or liquid products have a number of advantages: They are easier to use dosing and handling and have advantages due to their compact structure Storage and transportation. There is therefore an extremely wide range of prior art Detergent tablets, which can also be found in an extensive patentlite ratur precipitates. The developers of tablet-shaped products were recognized early on Idea came to be about differently composed areas of the molded body correct ingredients only under defined conditions in the washing or cleaning cycle release, in order to improve the cleaning success. Here, in addition to the well-known core / shell tablets and ring / core tablets ins  special multi-layer molded articles, which are used today for many areas of the Wa cleaning and hygiene.

Multi-phase cleaning tablets for the toilet are described, for example, in EP 055 100 (Jeyes Group). This document discloses blocks of toilet detergents that ei molded body from a slowly soluble detergent composition grasp, in which a bleach tablet is embedded. This document reveals at the same time the most diverse designs of multi-phase molded articles. The production the molded body is made according to the teaching of this document either by inserting a ver pressed bleach tablets into a mold and poured this tablet around with the Reini detergent composition, or by pouring in part of the detergent composition into the mold, followed by inserting the compressed bleach tablet and possibly subsequent pouring over with further detergent composition. The Pouring of prefabricated troughs is neither described nor near in this document placed.

EP 481 547 (Unilever) also describes multi-phase detergent tablets which to be used for automatic dishwashing. These moldings have the Form of core / shell tablets and are made by gradually compressing the stock parts manufactured: First, a bleach composition is pressed into an egg nem molded body, which is in a matrix half-filled with a polymer composition is placed, which is then filled with additional polymer composition and with a a bleach molded article provided with a polymer jacket is pressed. The procedure will then repeated with an alkaline detergent composition so that a three-phase molded body results. About the possibility of substances via a path Introducing melt into shaped bodies is not described in this document.

The aspect of "controlled release" of ingredients, like to translate as "controlled release" called, was and is also in the field of washing and cleaning cleaning agents worked intensively, so that this also a variety of Publi conditions exist. Beat in the field of washing and cleaning active moldings  most of the fonts are used by disintegration aids or shower systems release certain areas of the body before, while the slower release individual components, e.g. B. by coating, wrapping or deliberate release occupies a rather subordinate position.

The present invention was based on the object of a production method for multiphase Provide detergent tablets, which allows molded articles generate a targeted release of certain ingredients at predeterminable time enable points in the washing and cleaning cycle. In particular, the inventions Process according to the invention detergent tablets can be produced, which characterized by excellent storage and transport stability and the opposite performance superior to conventional products in a wide variety of applications areas can show. Another requirement for the method to be provided was therefore in the fact that it is with respect to the detergent tablets to be produced maximum freedom of formulation for a wide variety of applications enables.

It has now been found that detergent tablets with the ge desired properties in a flexible and simple way, if one Manufacture moldings that have a trough, which subsequently with a melting dis persion or emulsion of certain active substances is poured out.

The object of the present invention is therefore a process for the production of multi-phase detergent tablets, which comprises the steps

• a) pressing a particulate premix into shaped bodies which have a trough point,
• b) Preparation of a melt suspension or emulsion from a coating substance, the one Has melting point above 30 ° C and one or more dispersed in it or emulsified active ingredient (s),
• c) Filling the mold bodies with the melt suspension or emulsion at Tempe temperatures above the melting point of the coating substance  
• d) cooling and optional post-treatment of the filled detergents and cleaning agents molded body

includes.

Process step a)

The particulate premix to be compressed can be used as desired Purpose of the washing and cleaning produced by the inventive method shaped agent usually contained in washing and cleaning agents Contain ingredients in varying amounts. In particular substances from the group of Surfactants, builders and complexing agents, bleach, bleach Activators, the enzymes, the polymers as well as the colors and fragrances can be selected in advance be included in the mix. However, certain substances from the groups mentioned can be targeted omitted from the premix and added to the melt suspension or emulsion of process step b) can be incorporated. Depending on the choice of wrapping material and active substance can be produced in this way, shaped articles containing certain active substances Release from the molded article early or with a time delay.

Preferred ingredients of the particulate premix are substances from the group of Builder. In addition to the wash-active substances, such builders are the most important in Detergents and cleaning agents. In the manufactured according to the invention Detergent tablets can all usually be in detergents and Builders used in cleaning agents may be included, in particular thus zeolites, sili kate, carbonates, organic cobuilders and - where there are no ecological prejudices against their Use exist - also the phosphates. The builders mentioned can also be used in surfactants Free moldings are used, so that it is possible according to the invention, moldings produce that can be used for water softening.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} . H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ . yH ₂ O is preferred, wherein β-sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of 1: 2 to 1: 3, 3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-ray radiation which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a release delay compared to conventional water glasses, are described for example in the German patent application DE-A-44 00 024 be. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

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

n Na ₂ O. (1-n) K ₂ O. Al ₂ O ₃ . (2-2.5) SiO ₂ . (3.5 - 5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granule Ren compound used, as well as a kind of "powdering" to compress the whole the mixture are used, usually both ways to incorporate the Zeolite can be used in the premix. Suitable zeolites have a middle part size of less than 10 µm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyro, are particularly suitable phosphates and especially the tripolyphosphates.

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 re, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adi Pinic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of the sen.

Alkali carriers can be present as further constituents. Alkali is considered to be an alkali carrier metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, alkali silicates, alkali metasilicates, and mixtures of the aforementioned substances  fe, for the purposes of this invention preferably the alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can be used.

If, according to the process of the invention, shaped articles for machine dishes Rinses are made, water-soluble builders are preferred because they are on dishes and hard surfaces tend less to form insoluble residues the. Usual builders that are used in the context of the inventive production of mechanical Dishwashing detergent between 10 and 90 wt .-% based on the pre-pressed the low molecular weight polycarboxylic acids and their salts the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, Phosphates and silicates. Are preferred for the production of moldings for the ma rapid dishwashing trisodium citrate and / or pentasodium tripolyphosphate and / or Sodium carbonate and / or sodium bicarbonate and / or gluconate and / or silicate Builder from the class of disilicate and / or metasilicate used. Particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate. A builder system that is a mixture of tripolyphos is also particularly preferred contains phate and sodium carbonate and sodium disilicate.

Regardless of the intended use of the Ver drive manufactured detergent tablets contains the ver in step a) pressed particulate premix builder usually in amounts of 20 to 80 wt .-%, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the premix.

In addition to the builders described above, the premix can also be used mentioned contain detergent substances, especially for detergent tablets are important ingredients. Depending on the molded body to be produced, the answer the questions of whether and if so which surfactants to use, different answers possible Lich. Typically, molded articles for washing textiles can be different Most surfactants from the groups of anionic, nonionic, cationic and amphote contain surfactants, while moldings for machine dishwashing preferably  They only contain low-foaming non-ionic surfactants and water softening tablets or bleach tablets are free of tensides. The professional are at the incorporation on the surfactants in the premix to be pressed in terms of freedom of formulation no limits.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins having an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is in 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-sulfofatty acids (ester sulfonates), e.g. B. the α sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce The mono-, di- and triesters as well as their mixtures are to be understood as Rinestern, as 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. Before pulled sulfated fatty acid glycerol esters are the sulfonation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Ca. pric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemically based, straight-chain alkyl radical which has a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

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

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

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

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

In the context of the present invention, the production of detergent tablets is before that 5 to 50 wt .-%, preferably 7.5 to 40 wt .-% and particularly 10 to 20 % By weight of anionic surfactant (s), based in each case on the weight of the shaped body.

When selecting the anionic surfactants that are used in the washing and Detergent tablets are used, the freedom of formulation does not stand in the way. Preferred detergent tablets have However, a soap content of 0.2 wt .-%, based on the total weight of the Molded body, exceeds. The preferred anionic surfactants are Alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets 2 up to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight Fatty alcohol sulfate (s), each based on the weight of the molded body.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a linear or preferably 2-methyl branching may be or linear and methyl branched radicals in the mixture, as they are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from Alko fetch native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol 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.

Another class of preferred non-ionic surfactants, either alone or non-ionic surfactant or in combination with other non-ionic surfactants are set, are alkoxylated, preferably ethoxylated or ethoxylated and propoxy lated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 are described or preferably according to the in the international Patent application WO-A-90/13533 can be prepared.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Applicable alkyl polyglycosides are generally sufficient NEN formula RO (G) Z, in which R represents a linear or branched, especially in 2- Position of methyl-branched, saturated or unsaturated, aliphatic radical with 8 to 22, preferably means 12 to 18 carbon atoms and G is the symbol which is for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z lies between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1, 1 and 1.4.

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

The detergent tablets according to the invention can preferably be alkyl Contain polyglycosides, with APG contents of the molded body being above 0.2% by weight on the entire molded body, are preferred. Particularly preferred washing and cleaning molded article bodies contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 up to 5% by weight and in particular from 0.5 to 3% by weight.

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 alka nolamides may be suitable. The amount of these nonionic surfactants is preferred  not more than that of the ethoxylated fatty alcohols, especially not more than that Half of it.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in the RCO for an aliphatic acyl radical with 6 to 22 carbon atoms, R1 for What serstoff, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for egg a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 is up to 10 hydroxyl groups. The polyhydroxy fatty acid amides are Known substances, usually 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 can.

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 R2 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] representing 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, at 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 the international application WO-A-95/07331 by reaction with fatty acids thylesters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fat acid amides are transferred.

In principle, all surfactants can also be used as ten sides in the production of moldings for automatic dishwashing. For this application, preference is given to the nonionic surfactants described above and above all the low-foaming nonionic surfactants. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention, the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as, for example, C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ and C ₁₈ alcohols). As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used for the purposes of the invention. Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

In the manufacture of moldings for automatic dishwashing with the help of the Process variants according to the invention are preferred, in which the step  a) pressed particulate premix surfactant (s), preferably nonionic (s) Ten sid (e), in amounts of 0.5 to 10 wt .-%, preferably from 0.75 to 7.5 wt .-% and ins contains in particular from 1.0 to 5% by weight, based in each case on the premix.

In addition to the ingredients from the group of builders and ten described above Side, the premix to be pressed can contain other common ingredients of washing and Detergents, especially from the groups of disintegration aids, bleach agents, bleach activators, enzymes, fragrances, perfume carriers, fluorescent agents, dyes, Foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors, corrosion inhibitors, etc. included. This stuff fe, just like the above-mentioned builders and surfactants also about the process step b) can be processed are described below.

In order to facilitate the disintegration of highly compressed moldings, it is possible to disintegrate on aids, so-called tablet disintegrants, to incorporate them into the disintegration to shorten times. Tablet disintegrants or accelerators of disintegration are used according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical tech nologie "(6th edition, 1987, pp. 182-184) understood auxiliary substances necessary for the rapid disintegration of tablets in water or gastric juice and for the release of pharmaceuticals in resorbier ensure a form.

These substances, which are also referred to as "explosives" due to their effect, ver increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known disintegration aid medium are, for example, carbonate / citric acid systems, but also other organic ones Acids can be used. Swelling disintegration aids are, for example synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modes natural substances such as cellulose and starch and their derivatives, alginates or casein Derivatives.  

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

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

The cellulose used as disintegration aid is preferably not in finely divided form ger form used, but before mixing to the premixes to be pressed in transferred a coarser form, for example granulated or compacted. Washing and cleaning molded article, the disintegrants in granular or optionally co-granulated  Contain form, are in the German patent applications DE 197 09 991 (Stefan Her drew) and DE 197 10 254 (Henkel) and international patent application WO98 / 40463 (Henkel). These writings are also detailed information on the production of granu lined, compacted or cogranulated cellulose disintegrant. The part The sizes of such disintegrants are usually above 200 μm, preferably to at least 90% by weight between 300 and 1600 µm and in particular at least 90 % By weight between 400 and 1200 microns. The above and in the cited scripture The coarser disintegration aids described in more detail on the basis of cellulose are described in Within the scope of the present invention, preferably used as a disintegration aid and commercially, for example, under the name Arbocel® TF-30-HG from the company Rettenmaier available.

As a further disintegrant based on cellulose or as part of this compo microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged. One after subsequent disaggregation of the microfine celluloses resulting from the hydrolysis manufactures the microcrystalline celluloses, which have primary particle sizes of approx. 5 µm and for example compactible to granules with an average particle size of 200 microns are.

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, peroxypyrophosphate, 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 washing textiles, the use of sodium percarbonate is preferred, irrespective of which other ingredients are contained in the moldings. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as. B. Dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimido peroxycaproic acid [Phtha loiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyacid, diperoxyacid Diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.

Chlorine or. Can also be used as bleaching agents in moldings for automatic dishwashing Bromine-releasing substances are used. Among the appropriate chlorine or bromine releasing materials come for example heterocyclic N-bromine and N- Chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5- dimethylhydanthoin are also suitable.

To be a better choice when washing or cleaning at temperatures of 60 ° C and below To achieve the greatest bleaching effect, bleach activators can be pre-pressed be mixed in. As bleach activators, compounds that are under Perhy aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid ben, are used. Suitable substances are the O and / or N-acyl groups of the ge  mentioned number of carbon atoms and / or optionally substituted benzoyl groups. Before multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, are added (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5- triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially special n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid reanhydrides, especially 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 can also bleaching catalysts mentioned are incorporated into the moldings. With these fabrics are bleach-enhancing transition metal salts or transition metal complexes xe such as Mn, Fe, Co, Ru or Mo salt complexes or -carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are known as Bleichka Talysators can be used.

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 proteases obtained from Bacillus lentus are used. Are there 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 cellulase-containing Mi of particular interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable. The enzymes can be adsorbed on carriers and / or in Envelope substances must be embedded to protect them against premature decomposition. The amount of the enzymes, enzyme mixtures or enzyme granules in the inventive Shaped bodies can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 % By weight.  

In addition, the premix to be pressed can be used for the production of detergent form bodies also contain components that make oil and fat washable from textiles influence positively (so-called soil repellents). This effect is particularly evident if a textile is soiled that has already been used several times with an inventive ß detergent containing this oil and fat-dissolving component has been washed. To The preferred oil and fat dissolving components include, for example, nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of Methoxyl groups from 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15 % By weight, in each case based on the nonionic cellulose ether, and those from the prior art known polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene Lenglykolterephthalaten or anionically and / or nonionically modified derivatives of this. Of these, the sulfonated derivatives of phthalic acid and of terephthalic acid polymers.

The premix to be pressed can be produced when manufacturing textile detergent tablets wants, as optical brighteners derivatives of diaminostilbenedisulfonic acid or their Contain alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino- 1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or a similar structure Ver bonds that replace the morpholino group with a diethanolamino group, a methyl wear amino group, an anilino group or a 2-methoxyethylamino group. Farther brighteners of the substituted diphenylstyryl type may be present, e.g. B. 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 above mentioned brighter can be used.

Dyes and fragrances can be added to the premix in the process according to the invention to improve the aesthetic impression of the resulting products and the In addition to the softness performance, consumers are visually and sensory "typical and unmatched interchangeable "product. As perfume oils or fragrances can individual fragrance compounds, e.g. B. the synthetic products of the ester, ether,  Aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compound Solutions of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexylacetate, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylacetat, Li nalylbenzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropionate, sty rallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. B. the linear alkanals with 8-18 C atoms, citral, citronellal, citro nellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and Bourgeonal, to the Ketones e.g. B. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols Anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, among the Hydrocarbons mainly belong to the terpenes like limonene and pinene. Prefers however, mixtures of different odoriferous substances are used, which together form one generate a speaking fragrance. Perfume oils of this type can also contain natural odoriferous substances contain as accessible from plant sources, e.g. B. pine, citrus, jasmine, Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the premix, but it can also be advantageous to apply the fragrances on carriers, which the adhesion of the perfume on the Reinforce laundry and through a slower fragrance release for long-lasting fragrance Take care of textiles. Cyclodextrins, for example, have proven to be such carrier materials lasts, the cyclodextrin-perfume complexes additionally with other auxiliaries can be coated.

In order to improve the aesthetic impression of the agents produced according to the invention, the premix (or parts thereof) can be colored with suitable dyes. Be preferred dyes, the selection of which is not difficult for the person skilled in the art high storage stability and insensitivity to the other ingredients the means and against light and no pronounced substantivity towards textile fibers or dishes so as not to stain them.  

Shaped body for the mechanical cleaning of dishes according to the invention process, the premix to be pressed can be used for protection the washware or the machine contain corrosion inhibitors, especially silver protective agents in the field of automatic dishwashing are of particular importance. The known substances of the prior art can be used. Generally can before all silver protection agent selected from the group of triazoles, benzotriazoles, Bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole are particularly preferred and / or alkylaminotriazole. You will also often find it in detergent formulations agents containing active chlorine, which can significantly reduce the corrosion of the silver surface nen. Chlorine-free cleaners especially contain oxygen and nitrogenous organic ones redox-active compounds, such as di- and trihydric phenols, e.g. B. Hydroquinone, Brenz catechin, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives thereof Connection classes. Also salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Are preferred here in the transition metal salts, which are selected from the group of manganese and / or Cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or Manganese and manganese sulfate. Zinc compounds can also be used to prevent the Corrosion can be used on the wash ware.

As described above, the premix can consist of a wide variety of substances be composed. Regardless of the composition of the process step a) Premixes to be injected can contain physical parameters of the premixes be chosen that result in advantageous molded properties.

Thus, in preferred variants of the method according to the invention, the steps a) compressed particulate premixes bulk densities above 600 gl, preferably have above 700 g / l and in particular above 800 g / l.  

The particle size in the premixes to be compressed can also be advantageous for obtaining more shaped body properties can be set. In preferred methods, the in Step a) pressed the particulate premix to a particle size distribution in which less than 10% by weight, preferably less than 7.5% by weight and in particular less than 5% by weight of the particles are larger than 1600 μm or smaller than 200 μm. Here are narrower particle size distributions more preferred. Particularly advantageous process Rianten are characterized in that the particulate pressed in step a) Premix has a particle size distribution in which more than 30% by weight, preferably as more than 40 wt .-% and in particular more than 50 wt .-% of the particles a part have a size between 600 and 1000 µm.

When carrying out process step a), the process according to the invention is not limited to that only a particulate premix to a well shape body is pressed. Rather, method step a) can also be expanded to that effect tern that one produces in a manner known per se multilayered shaped articles by prepares two or more premixes which are pressed together. Here is the first pre-filled slightly pre-compressed to a smooth and parallel to the molding to get the top that runs through the floor, and after filling in the second pre mixes to the finished molded body. With three- or multi-layer molded articles After each premix addition, a further pre-compression takes place, before after adding the last premix, the molded body is finally pressed.

Due to the increasing technical complexity, there is a maximum of two layers in practice term shaped body preferred. Already in this intermediate step in the Ver Can drive from the distribution of certain ingredients on the individual layers Advantages are achieved.

For example, methods are preferred in which in step a) two-layer form bodies that have a trough are produced by two different particles shaped premixes are pressed together, one of which is one or more Bleach and the other contains one or more enzymes. Not just this separation  of bleach and enzymes can bring benefits, including the separation of bleach and optional bleach activators can be advantageous so that fiction Moderate process variants are preferred in which in step a) two-layer moldings per, which have a trough, are produced by two different particles shaped premixes are pressed together, one of which is one or more Bleach and the other contains one or more bleach activators.

In order to produce the shaped bodies with a trough in process step a), the premix is in a so-called die between two stamps compressed into a solid compressed. This process, which is briefly referred to below as tabletting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and expelling.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined. The constant dose tion even at high molding throughputs is preferably a volumetric Dosage of the premix reached. In the further course of tabletting, the Upper stamp the premix and continues to lower towards the lower stamp. At this compression, the particles of the premix are pressed closer together, whereby the void volume within the filling between the punches continuously decreases takes. From a certain position of the upper stamp (and thus from a certain Pressure on the premix) begins the plastic deformation, in which the particles come together flow and the molded body is formed. Depending on the physical Properties of the premix are also crushed and part of the premix particles sintering of the premix occurs at even higher pressures. With increasing Pressing speed, i.e. high throughput, becomes the phase of elastic deformation mung continuously shortened, so that the resulting molded body more or less large Can have cavities. The final step of tableting is the finished form body pressed out of the die by the lower punch and by subsequent ones Transport equipment transported away. At this point, only the weight of the  Shaped body finally determined because the compacts due to physical processes (Stretching, crystallographic effects, cooling etc.) their shape and size still change can.

Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only the waiter stamp used to build up pressure, also the lower stamp moves during the Pressing process towards the upper punch, while the upper punch presses down. For Small production quantities are preferably used with eccentric tablet presses which the one or more stamps are attached to an eccentric, which in turn on one Axis is mounted with a certain rotational speed. The movement of this Press ram is comparable to the way a conventional four-stroke engine works. The Ver pressing can be done with one upper and one lower stamp, but several can also be used Stamp be attached to an eccentric disc, the number of die holes is expanded accordingly. The throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, in which on a so-called called matrix table a larger number of matrices is arranged in a circle. The The number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available. Each die on the die table is a top and bottom stamp assigned, again the pressing pressure active only by the upper or lower stamp, but can also be built up by both stamps. The matrix table and the Stamps move around a common vertical axis, the stamp with the help of rail-like cam tracks during the circulation in the positions for filling tion, compression, plastic deformation and discharge. In the places, at which require a particularly serious raising or lowering of the stamp (Filling, compacting, ejecting), these cam tracks are reduced by additional thrust pieces, low-tension rails and lifting tracks supported. Filling the Matri ze takes place via a rigidly arranged feed device, the so-called filling shoe is connected to a reservoir for the premix. The pressure on the front mixture can be individually adjusted via the press paths for upper and lower punches, whereby the  Pressure build-up by rolling the punch shaft heads past adjustable pressure rollers happens.

Rotary presses can also be equipped with two filling shoes to increase throughput be, whereby only a semicircle is run through to produce a tablet got to. Several filling shoes are used to produce two- and multi-layer molded articles arranged one behind the other without the slightly pressed first layer before the next Filling is ejected. Through appropriate process control, too Shell and dot tablets can be produced, which have an onion-shell-like structure, where in the case of the point tablets, the top of the core or core layers does not have is covered and thus remains visible. Rotary tablet presses are also available with single or Multiple tools can be equipped so that, for example, an outer circle with 50 and one inner circle with 35 holes can be used for pressing at the same time. The throughput ze modern rotary tablet presses are over one million tablets per hour.

Within the scope of the present invention for carrying out process step a) ge Suitable tableting machines are available, for example, from the Apparatebau company Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Zell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschi nenbau AG, Bern (CH) and Courtoy N.V., Halle (BE / LU). Is particularly suitable for for example the hydraulic double pressure press HPF 630 from LAEIS, D.

The moldings can ge in a predetermined spatial shape and a predetermined size be manufactured. Practically all sensibly manageable designs come as a spatial form conditions, for example the formation as a board, the shape of a bar or bar, Cubes, cuboids and corresponding room elements with flat side surfaces and esp special cylindrical configurations with circular or oval cross-section. The se last embodiment covers the presentation form from the tablet to compact Cylinder pieces with a ratio of height to diameter above 1.  

The spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of standard household washing machines or the dosing chamber customary dishwashers adapted so that the moldings without metering aid can be dosed directly into the induction chamber, where they are during the induction dissolve the process, or from where it is released during the cleaning process the. It goes without saying that the detergent tablets are also used easily possible via dosing aids.

An essential feature of the method according to the invention is that the shaped bodies, which are produced in step a) have a trough which in step c) with the in Step b) prepared melt suspension or emulsion is filled. This hollow can have a wide variety of geometric configurations, the geome tie of the trough is independent of the geometry of the molded body. For example round shaped body with round, elliptical, three, four, five or polygonal mul that conceivable. The trough shapes mentioned can also be rectangular or square The shaped bodies are realized, the corners of the shaped bodies being rounded can.

The side walls of the trough can also run differently - conceivable here all transitional forms from the vertical side wall to the flatter one Straight or curved trough walls. Particularly suitable troughs Geometries are described in the earlier German patent application 198 22 973.9 (Henkel) ben. The geometric factors disclosed in this document preferably also apply to the Trough moldings produced in step a) of the method according to the invention.

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

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, the break of the shaped body, D is the shaped body diameter in meters and t is the height the molded body.

Process step b)

In process step b), a melt suspension or emulsion is made from an enveloping sub punch that has a melting point above 30 ° C and one or more in it dispersed or suspended active ingredient (s). Suitable as active substance (s) in principle, all the contents usually used in detergents and cleaning agents substances, especially those already mentioned above as optional ingredients of the material to be pressed Premixed ingredients described and described in detail. Particularly preferred Active substances are described again separately below.

Coating substances

To the coating substances that form the "basis" of the melt suspension or -emulsion form, there are various requirements, on the one hand the melt or solidification behavior, but also the material properties cover in the solidified area at ambient temperature. Because the wrapping the active substances included in it permanently during transport or storage To protect environmental influences, it must have a high stability compared to, for example Packaging or transport. The wrapping should thus either at least partially elastic or at least plastic properties have to to a shock load occurring due to elastic or plastic deformation to react and not to break. The wrapper should have a melting range (Solidification range) in such a temperature range in which the enveloping active substances are not exposed to excessive thermal stress. Ande on the other hand, the melting range must be sufficiently high to be at least light increased temperature still effective protection for the enclosed active substances Offer. According to the invention, the coating substances have a melting point above 30 ° C.  

It has proven to be advantageous if the coating substance does not have a sharply defined one Melting point shows how it usually occurs with pure, crystalline substances, but may have a melting range spanning several degrees Celsius.

The coating substance preferably has a melting range which is between approximately 45 ° C. and is about 75 ° C. In the present case, this means that the melting range within the specified temperature interval occurs and does not denote the width of the Melting range. The width of the melting range is preferably at least 1 ° C. preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances, which usually melt above 40 ° C without decomposition and a little above the Melting point are relatively low viscosity and not stringy. You assign one strongly temperature-dependent consistency and solubility.

According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as Petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.  

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. Connections can also be used as covering materials from other classes of substances that meet the stated softening point requirements fulfill. Suitable synthetic compounds have, for example, higher esters of Phthalic acid, especially dicyclohexyl phthalate, commercially available under the name Unimoll® 66 (Bayer AG) is available. Synthetic waxes made of are also suitable lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which under the Name Cosmacol® ETLP (Condea) is available. Conversely, synthetic or Semi-synthetic esters from lower alcohols with fatty acids from native sources can be used. Tegin® 90 (Goldschmidt), for example, falls into this class of substances Glycerol monostearate palmitate. Also shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH) can be used according to the invention as a covering material.

The waxes, for example, are also included in the scope of the present invention so-called wax alcohols. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols usually with about 22 to 40 carbon atoms. The Wax alcohols, for example, come in the form of wax esters of higher molecular weight Fatty acids (wax acids) as the main component of many natural waxes. examples for Wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or Melissyl alcohol. The coating of the solid particles coated according to the invention can optionally also contain wool wax alcohols, including triterpenoid and Steroidal alcohols, for example lanolin, means that, for example, under the Trade name Argowax® (Pamentier & Co) is available. Also at least in part can be used as part of the envelope within the scope of the present invention Fatty acid glycerol esters or fatty acid alkanolamides, but optionally also water-insoluble ones or only slightly water-soluble polyalkylene glycol compounds.

The coating substance used in process step b) according to the invention preferably contains predominantly paraffin wax. This means that at least 50% by weight of the Wrapping, preferably more, consist of paraffin wax. Are particularly suitable Paraffin wax contents in the coating of about 60% by weight, about 70% by weight or about 80  % By weight, with even higher proportions of, for example, more than 90% by weight in particular are preferred. In a special embodiment of the invention, the casing is made made exclusively from paraffin wax.

Paraffin waxes have a frame compared to the other natural waxes mentioned The present invention has the advantage that in an alkaline There is no hydrolysis of the waxes in the detergent environment (as is the case, for example, with the wax esters can be expected), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this melting temperature in the detergent fleet undesirable wax residues on the surfaces to be cleaned or the goods to be cleaned. Such Wax residues usually lead to an unsightly appearance of the cleaned Surface and should therefore be avoided.

The coating substance used in step b) according to the invention preferably contains at least a paraffin wax with a melting point of about 50 ° C to about 55 ° C.

The content of the paraffin wax used is preferably at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes if possible high. The more solid wax components in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing share of solid wax components increase the resilience of the coating to impact or Rubbing against other surfaces, resulting in longer-lasting protection of the encased Leads active substances. High proportions of oils or liquid wax components can lead to a Weaken the envelope, which opens pores and the enveloped Active substances are exposed to the environmental influences mentioned above.  

In addition to paraffin as the main constituent, the coating can also have one or more of the above mentioned waxes or wax-like substances. Basically, that should be the Envelope-forming mixture should be such that the envelope is at least largely is insoluble in water. The solubility in water should be at a temperature of around 30 ° C Do not exceed 10 mg / l and are preferably below 5 mg / l.

In any case, however, the coating should have the lowest possible water solubility, also in Water with elevated temperature, have a temperature-independent release of the to avoid coated active substances as much as possible.

The principle described above serves to delay the release of ingredients (the Active substances in the melt suspension or emulsion) at a certain time in the cleaning cycle and can be used particularly advantageously when using in the main wash cycle lower temperature (for example 55 ° C) is rinsed, so that the active substance from the Melt embedding is only released in the rinse cycle at higher temperatures (approx. 70 ° C) becomes.

However, the principle mentioned can also be reversed in that the active ingredient (s) are not delayed from the wrapping, but are released faster. This can be seen in Achieve method according to the invention in a simple manner in that as coating substances not release delay, but release accelerators are used, so that the im Molded solidified melt suspension or emulsion does not dissolve more slowly than that pressed molded body, but faster. In contrast to those described above poorly water-soluble dissolution retarders, preferred dissolution accelerators are good water soluble. The water solubility of the dissolving accelerators can be determined by certain additives be significantly increased, for example by incorporating easily soluble Salts or effervescent systems. Such solvent-accelerated coating substances (with or without Additions of further solubility improvers) lead to a rapid release of the enclosed active substances at the beginning of the cleaning cycle.  

As a release accelerator, i.e. coating substances for the accelerated release of the active substance stamping from the core cast into the molded body, the first are particularly suitable The synthetic waxes mentioned from the group of polyethylene glycols and Polypro pylene glycols.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are polymers of ethylene glycol which have the general formula III

H- (O-CH ₂ -CH ₂ ) _n -OH (III)

are sufficient, where n can have values between 1 (ethylene glycol) and over 100,000.

The decisive factor in evaluating whether a polyethylene glycol can be used according to the invention is the state of aggregation of the PEG, d. H. the melting point of the PEG must be above 30 ° C, so that the monomer (ethylene glycol) and the lower oligomers with n = 2 up to approx. 16 cannot be used because they have a melting point below 30 ° C. The higher molecular weight polyethylene glycols are polymolecular, i.e. they consist of Collective macromolecules with different molecular weights. For polyethylene glycol cole exist different nomenclatures that can lead to confusion. Technically It is common to state the average relative molecular weight after the anga be "PEG", so that "PEG 200" is a polyethylene glycol with a relative molecular weight of approx. 190 to about 210 characterized. According to this nomenclature are within the scope of the present Invention the technically common polyethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 are preferred.

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and a number follows the hyphen directly, which corresponds to the number n in the above-mentioned formula III. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-32, PEG-40, PEG-55, PEG 60, PEG-75, PEG-100, PEG-150 and PEG-180 can preferably be used according to the invention.

Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 540 (Union Carbide), Emkapol® 6000 (ICI Americas), Lipoxol® 3000 MED (HÜLS America), Polyglycol® E-3350 (Dow Chemical), Lutrol® E4000 (BASF) and the corresponding trade names with higher numbers.

Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula IV

are sufficient, where n values can be between 1 (propylene glycol) and approx. 1000. Similar Lich, as with the PEG described above, it comes to the assessment whether a poly propylene glycol can be used according to the invention on the physical state of the PPG, d. H. the melting point of the PPG must be above 30 ° C so that the monomer (propy lenglycol) and the lower oligomers with n = 2 to approx. 15 cannot be used since they have a melting point below 30 ° C.

In addition to the PEG and PPG which can preferably be used as solution-accelerated coating substances Of course, other substances can also be used, provided that they are sufficiently high Have water solubility and have a melting point above 30 ° C.

The melt suspension or emulsion produced in process step b) can vary de Contain quantities of coating substance, auxiliary substances and active substance to be coated. In preferred processes make the coating substance 20 to 95 wt .-%, preferably 30 to 70 % By weight and in particular 40 to 50% by weight of the melt suspensions produced in step b) sion or emulsion.  

Active substance (s)

The active ingredients to be incorporated into the melt suspension or emulsion can be used in the Processing temperature in both solid and liquid form, as long as the Melt suspension or emulsion below its melting point or solidification point is in solid form in order to permanently fill the trough.

The active ingredients contained in the melt suspension or emulsion meet in invent detergent tablets produced in accordance with certain tasks. By separating certain substances or by accelerating or ver Delayed release of additional substances can result in washing or cleaning stung be improved. Active substances, which are preferred in the melt suspension or emul are incorporated, are such ingredients of washing and cleaning agents means that are crucially involved in the washing or cleaning process.

In preferred processes, therefore, the active ingredient (s) are those in step b) provided melt suspension or emulsion selected from the group of enzymes, Bleaching agents, bleach activators, surfactants, corrosion inhibitors, scale inhibitors, cobuil the and / or fragrances.

By incorporating surfactants into the melted shell material, one can Make melt suspension or emulsion, which in the finished washing and cleaning shaped detergent body additional wash-active at a predetermined time Provides substance. For example, according to the invention ß procedure Manufacture moldings for automatic dishwashing, the additional Only release the surfactant at temperatures which are common household dishwashers Only reach in the rinse aid. In this way there is an additional ten rinse aid sid is available, which accelerates the drainage of the water and so stains on Washware effectively prevented. With a suitable amount of solidified enamel suspension or emulsion in the moldings produced by the process according to the invention it is now possible to dispense with the use of additional rinse aid that is common today.  

Instead of separate dosing and dimensioning of two products, this is only a problem The addition of a molded article is required, which saves time, effort and costs.

In preferred processes, the active substance (s) is / are used in step b) provided melt suspension or emulsion selected from the group of nonionic Surfactants, especially the alkoxylated alcohols. These substances have been discussed above described in detail.

Another class of active substances that are particularly beneficial in the enamel Allow suspension or emulsion to be incorporated are bleaching agents. Here, washing and detergent tablets are produced, the bleach only when Errei Chen release certain temperatures, such as detergent tablets, the in advance Clean the wash cycle enzymatically and only release the bleach in the main wash cycle. Also Detergent tablets for machine dishwashing can be manufactured in such a way Rinse aid to release additional bleach and so difficult stains, for example Remove tea stains more effectively.

In preferred processes, the active substance (s) is / are used in step b) melt suspension or emulsion are selected from the group of oxygen or halogen bleach, especially chlorine bleach. These substances are also described in detail above.

Another class of compounds that are preferred as active substances in the enamel suspension or emulsion can be used, the bleach activators. Known Bleach activators are compounds that contain one or more N or O acyl groups hold, such as substances from the class of anhydrides, esters, imides and acylier ten imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylme thylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA. Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators cal peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms  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. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated tria Zinderivate, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acy gelled Glycolurile, in particular tetraacetylglycoluril (TAGU), N-acylimide, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol koldiacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well as acetylated sorbitol and mannitol as their mixtures (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose and acety gelled, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated Lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and Acyl lactams are also preferred. Combinations of conventional ones Bleach activators can be used.

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

Bleach activators from the group of multi-acylated alkylene are preferred diamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N- Nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight  up to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight on the entire means.

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

Fragrances can also be used as active substances in the melt suspension or emulsion incorporate. All fragrances described in detail above can be used as Active substance can be used. When fragrances are incorporated into the melting fluid sion or emulsion result in detergent tablets which cover the entire or release some of the perfume with a time delay. In this way, according to the invention Process, for example, moldings for automatic dishwashing can be manufactured in which the consumer opens the dishes even after cleaning the dishes the machine experienced the perfume note. This way the unwanted "Alkaline smell", which adheres to many automatic dishwashing detergents, can be eliminated.

Corrosion inhibitors can also be used as the active ingredient in the according to the invention Introduce the molded article produced by the process, referring to those familiar to the skilled worker Substances can be used. One has, for example, a deposit inhibitor Combination of enzyme (e.g. lipase) and lime soap dispersant proven.  

Regardless of the substance class that is used as an active ingredient, the make Active substance (s) usually 5 to 50% by weight, preferably 10 to 45% by weight and in particular special 20 to 40% by weight of the melt suspension produced in step b) or emulsion from.

Auxiliaries

At exceptionally low temperatures, for example at temperatures below 0 ° C, can break the casing when subjected to shock or friction. To the stability at such To improve low temperatures, the coating may contain additives be added. Suitable additives must be completely mixed with the melted Allow wax to mix, the melting range of the coating substances must not be significant change, must improve the elasticity of the casing at low temperatures, the In general, the casing is not permeable to water or moisture increase and must not increase the viscosity of the melt of the shell material to such an extent that processing becomes difficult or even impossible. Suitable additives that the Brittleness of an envelope consisting essentially of paraffin at low temperatures low temperatures, for example EVA copolymers, hydrogenated resin acid methyl esters, Polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.

Another useful additive when using paraffin as a coating is the addition of a small amount of a surfactant, for example a C _12-18 fatty alcohol sulfate. This addition results in a better wetting of the material to be embedded through the covering. It is advantageous to add the additive in an amount of about <5% by weight, preferably <about 2% by weight, based on the coating substance. The addition of an additive can in many cases lead to the fact that active substances can also be encased, which without additive additive usually form a tough, plastic body made of paraffin and partially dissolved active substance after the encapsulation material has melted.

In process step b) according to the invention, it can be advantageous to further coat the substance Add additives to, for example, early deposition of those to be wrapped To prevent active substances during cooling. The anti-settling agents that can be used for this,  which are also referred to as suspended materials are from the prior art, known for example from the manufacture of lacquer and printing inks. To move from plastic solidification area to solid sedimentation phenomena and Avoiding differences in the concentration of the substances to be encased is an option for example surface-active substances, waxes dispersed in solvents, Montmorillonites, organically modified bentonites, (hydrogenated) castor oil derivatives, soy lecithin, Ethyl cellulose, low molecular weight polyamides, metal stearates, calcium soaps or hydrophobicized silicas. Other substances that cause the effects mentioned come from from the groups of anti-floating agents and thixotropic agents and can be chemical as silicone oils (dimethylpolysiloxanes, methylphenylpolysiloxanes, polyether-modified Methylalkylpolysiloxanes), oligomeric titanates and silanes, polyamines, salts from long-chain Polyamines and polycarboxylic acids, amine / amide-functional polyesters or amine / amide functional polyacrylates are called.

Additives from the classes of substances mentioned are commercially extremely diverse available. Commercial products which are advantageous as part of the process according to the invention Additives that can be added are, for example, Aerosil® 200 (pyrogenic silicic acid, Degussa), Bentone® SD-1, SD-2, 34, 52 and 57 (Bentonit, Rheox), Bentone® SD-3, 27 and 38 (Hectorite, Rheox), Tixogel® EZ 100 or VP-A (organically modified smectite, Südchemie), Tixogel® VG, VP and VZ (Montmorillonite loaded with QAV, Südchemie), Disperbyk® 161 (Block copolymer, Byk-Chemie), Borchigen® ND (sulfo group-free ion exchanger, Borchers), Ser-Ad® FA 601 (Servo), Solsperse® (aromatic ethoxylate, ICI), Surfynol®- Types (Air Products), Tamol® and Triton® types (Rohm), Texaphor®963, 3241 and 3250 (polymers, Henkel), Rilanit® types (Henkel), Thixcin® E and R (castor oil derivatives, Rheox), Thixatrol® ST and GST (castor oil derivatives, Rheox), Thixatrol® SR, SR 100, TSR and TSR 100 (polyamide polymers, Rheox), Thixatrol® 289 (polyetsre polymer, Rheox) and the different M-P-A® types X, 60-X, 1078-X, 2000-X and 60-MS (organic Connections, Rheox).

The auxiliaries mentioned can vary in the process according to the invention Wrapping material and material to be wrapped are used in varying amounts.  

Usual concentrations for the anti-settling, anti-swimming, Thioxotropic and dispersing agents are in the range from 0.5 to 8.0% by weight, preferably between 1.0 and 5.0% by weight, and particularly preferably between 1.5 and 3.0% by weight, each based on the melt suspension or emulsion.

In the context of the present invention, therefore, methods are preferred in which the in Step b) prepared melt suspension or emulsion further auxiliaries from the group pe of anti-settling agents, floating agents, anti-floating agents, thixotropic agents and dis Pergierhilfsmittel in amounts of 0.5 to 8.0 wt .-%, preferably between 1.0 and 5.0 Wt .-%, and particularly preferably between 1.5 and 3.0 wt .-%, each based on the Melt suspension or emulsion.

Especially in the production of melt suspensions or emulsions that are active Containing substances that are liquid at the processing temperature, the use is speci eller emulsifiers advantageous. It has been shown that in particular emulsifiers from the Group of fatty alcohols, fatty acids, polyglycerol esters and polyoxyalkylene siloxanes are extremely suitable.

Under fatty alcohols the native fats or oils are converted to the corresponding ones Understand fatty acids (see below) available alcohols with 6 to 22 carbon atoms. These alcohols can vary depending on the origin of the fat or oil from which they are obtained are substituted or unsaturated in places in the alkyl chain.

In process step b) according to the invention, the emulsifiers used are therefore preferably C _6-22 fatty alcohols, preferably C _8-22 fatty alcohols and in particular C _12-18 fatty alcohols, with particular preference given to C _16-18 fatty alcohols.

All of vegetable or animal oils and fats can also be used as emulsifiers obtained fatty acids are used. The fatty acids can be independent of theirs Physical state saturated or mono- to polyunsaturated. Even with the unsaturated The fatty acids are the solid species at room temperature compared to the liquid or  pasty preferred. Of course, not only "pure" fatty acids can be used but also the technical fat obtained from the splitting of fats and oils acid mixtures, these mixtures again being clearly preferred from an economic point of view are.

For example, emulsifiers can be used in the context of the present invention use individual species or mixtures of the following acids: caprylic acid, pelargonic acid, approx pric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, Arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, 10-undecenoic acid, Petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, α- and β-eläosterainic acid, gadoleic acid, erucic acid, brassidic acid. Of course the fatty acids with an odd number of carbon atoms can also be used, for example undes canoic acid, Tridec 13621 00070 552 001000280000000200012000285911351000040 0002019851426 00004 13502anoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosane acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid.

In preferred process _steps b), the emulsifier (s) used are C _6-22 fatty acids, preferably C _8-22 fatty acids and in particular C _12-18 fatty acids, with particular preference given to the C _16-18 fatty acids.

Particularly preferred emulsifiers in the context of the present invention are polyglycerol esters, in particular esters of fatty acids with polyglycerols. These preferred polyglycerol esters can be described by the general formula V.

in which R ¹ in each glycerol unit is independently H or a fatty acyl radical having 8 to 22 carbon atoms, preferably having 12 to 18 carbon atoms, and n is a number between 2 and 15, preferably between 3 and 10.

These polyglycerol esters are in particular with the degrees of polymerization n = 2, 3, 4, 6 and 10 known and commercially available. Since substances of the type mentioned also in cosmetic Formulations are widely used, some of these substances are also in the INCI Classified nomenclature (CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 '"Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 199i). This standard cosmetic work contains information on, for example Keywords POLYGLYCERYL-3-BEESWAX, POLYGLYCERYL-3-CETYL ETHER, POLYGLYCERYL-4-COCOATE, POLYGLYCERYL-10-DECALINOLEATE, POLY- GLYCERYL-10-DECAOLEATE, POLYGLYCERYL-10-DECASTEARATE, POLY- GLYCERYL-2-DIISOSTEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLY- GLYCERYL-10-DIISOSTEARATE, POLYGLYCERYL-2-DIOLEATE, POLY- GLYCERYL-3-DIOLEATE, POLYGLYCERYL-6-DIOLEATE, POLYGLYCERYL-10- DIOLEATE, POLYGLYCERYL-3-DISTEARATE, POLYGLYCERYL-6-DISTEARATE, POLYGLYCERYL-10-DISTEARATE, POLYGLYCERYL-10-HEPTAOLEATE, POLY- GYLCERYL-12-HYDROXYSTEARATE, POLYGLYCERYL-10-HEPTASTEARATE, POLYGLYCERYL-6-HEXAOLEATE, POLYGLYCERYL-2-ISOSTEARATE, POLY- GLYCERYL-4-ISOSTEARATE, POLY-GLYCERYL-6-ISOSTEARATE, POLY- GLYCERYL-10-LAURATE, POLY-LYCERYLMETHACRYLATE, POLYGLYCERYL- 10-MYRISTATE, POLYGLYCERYL-2-OLEATE, POLYGLYCERYL-3-OLEATE, POLYGLYCERYL-4-OLEATE, POLYGLYCERYL-6-OLEATE, POLYGLYCERYL-8- OLEATE, POLYGLYCERYL-10-OLEATE, POLYGLYCERYL-6-PENTAOLEATE, POLYGLYCERYL-10-PENTAOLEATE, POLYGLYCERYL-6-PENTASTEARATE, POLYGLYCERYL-10-PENTASTEARATE, POLYGLYCERYL-2-SESQUI- IOSOSTEARATE, POLYGLYCERYL-2-SESQUIOLEATE, POLYGLYCERYL-2- STEARATE, POLYGLYCERYL-3-STEARATE, POLYGLYCERYL-4-STEARATE, POLYGLYCERYL-8-STEARATE, POLYGLYCERYL-10-STEARATE, POLY- GLYCERYL-2-TETRAISETEARATE, POLYGLYCERYL-10-TETRAOLEATE, POLYGLYCERYL-2-TETRASTEARATE, POLYGLYCERYL-2-TRIISOSTEARATE, POLYGLYCERYL-10-TRIOLEATE, POLYGLYCERYL-6-TRISTEARATE. The Commercially available products from different manufacturers in the named plant  are classified under the keywords mentioned above, can be found in Process step b) according to the invention advantageously used as emulsifiers.

Another group of emulsifiers which can be used in process step b) according to the invention are substituted silicones which carry side chains reacted with ethylene or propylene oxide. Such polyoxyalkylene siloxanes can be described by the general formula VI

in which each radical R ¹ independently of one another for -CH ₃ or a polyoxyethylene or propylene group - [CH (R ² ) -CH ₂ O] _x H group, R ² for -H or -CH ₃ , x for one Number between 1 and 100, preferably between 2 and 20 and in particular less than 10, and n indicates the degree of polymerization of the silicone.

Optionally, the polyoxyalkylenesiloxanes mentioned can also be attached to the free OH groups of the Polxoxyethylene or polyoxypropylene side chains are etherified or esterified. The Unetherified and unesterified polymer from dimethylsiloxane with polyoxyethylene and / or Polyoxypropylene is used in the NCI nomenclature as DIMETHICONE COPOLYOL designated and is under the trade names Abil® B (Goldschmidt), Alkasil® (Rhönen- Poulenc), Silwet® (Union Carbide) or Belsil® DMC 6031 commercially available. The DIMETHICONE COPOLYOL ACETATE esterified with acetic acid (for example Belsil® DMC 6032, -33 and -35, Wacker) and the DIMETHICONE COPOLYOL BUTYL  ETHERS (eg KF352A, Shin Etsu) are part of the process step according to the invention b) can also be used as emulsifiers.

The same applies to the emulsifiers as to the wrapping materials and those to be wrapped Substances that can be used over a wide range. Usually, emulsifiers of the type mentioned make up 1 to 25% by weight, preferably 2 to 20% by weight and in particular 5 to 10% by weight of the weight of the melt suspension or emulsion from.

In preferred processes, the melt suspension produced in step b) contains or -emulsion additionally emulsifiers from the group of fatty alcohols, fatty acids, polyglycine Rine esters and / or polyoxyalkylene siloxanes in amounts of 1 to 20 wt .-%, preferably from 2 to 15% by weight, and particularly preferably from 2.5 to 10% by weight, in each case based on the melt suspension or emulsion.

Process step c)

In process step c), the separately produced mold bodies are separated with the prepared melt suspension or emulsion at temperatures above the melt temperature of the coating substance filled. The temperature of the melt to be filled can be there can be chosen at any level, with regard to temperature-sensitive ingredients but it is preferred that process step c) is carried out at temperatures which a maximum of 10 ° C, preferably a maximum of 5 ° C and in particular a maximum of 2 ° C above the Freezing temperature of the melt suspension or emulsion are.

The dosing of the melt suspension or emulsion into the well of the prefabricated Shaped body is preferably carried out by means of a piston metering pump, a pneumati pump, a peristaltic pump or a gear pump.

These pumps are familiar to a person skilled in the art for a wide variety of applications fig, so that depending on the composition of the melt suspension or emulsion it does not It is difficult to find the right pump in terms of size, material and mode of operation  to select. For melt suspensions or emulsions, surfactants, bleaches or Containing fragrances have proven particularly useful in piston metering pumps.

The moldings may have been pretreated before being filled with the melt to improve the adhesion of the melt in the trough. For example, it is possible to apply a suitable adhesive to the trough surfaces, which will ensure the adhesion of the Ensures melt on the molded body, so that during transport and handling of the molded body the solidified trough filling cannot separate from the molded body.

In terms of process technology, it is simpler and simpler that the trough moldings before loading fill with the melted suspension or emulsion to be warmed up to the adhesion of the to improve cooling melt. In this way, the cooling melt can at least at least partially penetrate into the edge areas of the trough, thus ensuring a solidification permanent and firm adhesive bond.  

Examples Manufacture of detergent tablets for automatic dishwashing Process step a): Production of moldings

By pressing two different premixes, two-layer rectangular moldings were produced, which had a trough in the form of a semi-ellipse. The molded bodies consisted of 75% by weight of the lower phase and 25% by weight of the upper phase. The following table shows the composition (in% by weight, based on the respective premix) of the two premixes and thus of the two different phases of the mold bodies:

Process step b): Preparation of melt suspensions / emulsions

By heating the casing material and stirring in the active substances and optional auxiliaries, three melt dispersions / emulsions SDE 1 to 3 were prepared, the composition (% by weight, based on the melt) of which is given in the table below:

Process step c): pouring the melt suspensions / emulsions into the moldings

The melt dispersions / emulsions produced in step b) were poured in the following weight ratios (data in% by weight, based on the fully filled molded article) into the trough molded articles produced in process step a), the molded articles being poured to 40 ° C had been heated:

Process step d): cooling and aftertreatment

The filled moldings were left to cool at room temperature and subsequently seperatly packaged.

The trough moldings with bleach core have an analog composition Shaped bodies in which the ingredients of the melt dispersion / emulsion individually and not were added to the premix in the form of a melt, significantly better cleaning properties stung, especially on tea stains.

The trough moldings with a surfactant core have an analogous composition Shaped bodies in which the ingredients of the melt dispersion / emulsion individually and not were added to the premix in the form of a melt, significantly better rinse aid stances, which manifest themselves in a significantly reduced formation of deposits on glasses ren.

The molded trough bodies with a fragrance core have a shape that is analogous bodies in which the ingredients of the melt dispersion / emulsion individually and not in Form of a melt were added to the premix, a significantly better perfume note when opening the machine.

All of the above tests were carried out in several commercial dishwashers NEN carried out by several test subjects, with the molded body in the dosing chamber placed in the machine and a 55 ° C program is run with the machine loaded was left. No detergent or rinse aid was used in any of the tests set.

The above examples show moldings in which the cast-in core is dissolved is released. In further examples, melt dispersions of n-methyl  Morpholinium acetonitrile methyl sulfate (MMA) in easily soluble coating substances provides evidence of the positive effects even with accelerated release.

Here, mold bodies were produced in accordance with process step a) described above. By heating the respective coating material and stirring in the active substance (MMA), melt dispersions SDE 4 to 8 were produced, the composition (% by weight, based on the melt) of which is given in the table below:

The melt dispersions were in the above-mentioned manner in the moldings filled and left to cool. Here, the moldings had a Ge before filling weight of 24 g and were filled with 1.3 g of the melt dispersion. The Reini performance of the molded bodies E4 filled with the melt dispersions SDE 4 to SDE 8 up to E8 was tested on tea stains. For this purpose, a tea stain was applied according to (1) produced and the soiled cups in a household dishwashing machine machine cleaned:

(1) Production of tea soiling

In a water treatment boiler, 161 cold city water (16 ° d) boil briefly heated. 96 g of black tea are left in the nylon net with the lid closed for 5 minutes ten draw and transfer the tea into a diving apparatus with heating and agitator.  

60 teacups are put into the prepared tea infusion 25 times at one-minute intervals at 70 ° C submerged. Then the cups are suspended and opened with the opening downwards Dried on a tray.

(2) Test results

The cleaning performance of the detergents for the soiling of tea according to the instructions under (1) was carried out visually by experts and graded, the rating "0" meaning no cleaning on a scale of 0-10 and "10" meaning complete removal of the stains. The teen notes were measured both for washing conditions 55 ° C / 16 ° d water hardness in the main rinse cycle (ie "hard conditions") and for 55 ° C / 3 ° d water hardness. A Miele G 590 with a universal program was used as the dishwasher. The table below shows the tea cleaning achieved in the middle E4 to E8 compared to an unfilled molded article V

The results show that the moldings E4 to E8 according to the invention are compared molded bodies V are far superior to tea cleaning.

Claims (23)

1. Process for the production of multi-phase detergent tablets, characterized by the steps

• a) pressing a particulate premix into shaped bodies which have a depression,
• b) preparation of a melt suspension or emulsion from a coating substance which has a melting point above 30 ° C. and one or more active substance (s) dispersed or suspended in it,
• c) filling the moldings with the melt suspension or emulsion at temperatures above the melting point of the coating substance,
• d) cooling and optional aftertreatment of the filled detergent tablets.

2. The method according to claim 1, characterized in that the pressed in step a) Particulate premix builder in amounts of 20 to 80 wt .-%, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the Premix contains. 3. The method according to any one of claims 1 or 2, characterized in that the in Step a) pressed particulate premix surfactant (s), preferably nonionic chemical surfactant (s), in amounts from 0.5 to 10% by weight, preferably from 0.75 to 7.5 % By weight and in particular from 1.0 to 5% by weight, in each case based on the premix, contains. 4. The method according to any one of claims 1 to 3, characterized in that in step a) pressed pre-mixed particulate a bulk density above 600 g / l, before preferably above 700 g / l and in particular above 800 g / l. 5. The method according to any one of claims 1 to 4, characterized in that in step a) pressed particulate premix has a particle size distribution at  which is less than 10% by weight, preferably less than 7.5% by weight and in particular less than 5% by weight of the particles are larger than 1600 μm or smaller than 200 μm. 6. The method according to claim 5, characterized in that the pressed in step a) Particulate premix has a particle size distribution in which more than 30% by weight, preferably more than 40% by weight and in particular more than 50% by weight the particles have a particle size between 600 and 1000 microns. 7. The method according to any one of claims 1 to 6, characterized in that in step a) multilayer moldings which have a trough in a manner known per se by placing several different particulate premixes on top of each other be pressed. 8. The method according to claim 7, characterized in that in step a) two-layer Shaped bodies, which have a trough, are produced by two different particulate premixes are pressed together, one of which is one or contains several bleaches and the other contains one or more enzymes. 9. The method according to any one of claims 7 or 8, characterized in that in step a) two-layer moldings which have a trough are produced by two different particulate premixes are pressed together, one of which one or more bleaches and the other one or more bleach activators contains. 10. The method according to any one of claims 1 to 9, characterized in that the enveloping sub punch in step b) has a melting range of 45 ° C to 75 ° C. 11. The method according to any one of claims 1 to 10, characterized in that the envelope Substance at least one paraffin wax with a melting range of 50 ° C to 55 ° C contains.   12. The method according to any one of claims 1 to 10, characterized in that the envelope substance at least one substance from the group of polyethylene glycols (PEG) and / or Contains polypropylene glycols (PPG). 13. The method according to any one of claims 1 to 12, characterized in that the envelope substance 20 to 95 wt .-%, preferably 30 to 70 wt .-% and in particular 40 to 50 % By weight of the melt suspension or emulsion produced in step b). 14. The method according to any one of claims 1 to 13, characterized in that the or the active substance (s) in the melt suspension or emulsion produced in step b) are selected from the group of enzymes, bleaching agents, bleach activators, surfactants, Corrosion inhibitors, scale inhibitors, cobuilders and / or fragrances. 15. The method according to claim 14, characterized in that the active ingredient (s) in the melt suspension or emulsion produced in step b) are selected from the group of nonionic surfactants, especially alkoxylated alcohols. 16. The method according to claim 14, characterized in that the active ingredient (s) in the melt suspension or emulsion produced in step b) are selected from the group of oxygen or halogen bleaches, especially chlorine bleach medium. 17. The method according to claim 14, characterized in that the active ingredient (s) in the melt suspension or emulsion produced in step b) are selected from the group of bleach activators, in particular from the groups of multiply acylated ten alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, in particular their n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl Morpholinium acetonitrile methyl sulfate (MMA).   18. The method according to any one of claims 1 to 17, characterized in that the or the active substance (s) 5 to 50% by weight, preferably 10 to 45% by weight and in particular 20 up to 40% by weight of the melt suspension or emulsion produced in step b) do. 19. The method according to any one of claims 1 to 18, characterized in that the in Step b) prepared melt suspension or emulsion from other auxiliaries Group of anti-settling agents, suspending agents, anti-floating agents, thixotropic agents and dispersing agents in amounts of 0.5 to 8.0% by weight, preferably between 1.0 and 5.0 wt .-%, and particularly preferably between 1, 5 and 3.0 wt .-%, respectively based on the melt suspension or emulsion. 20. The method according to any one of claims 1 to 19, characterized in that the in Step b) prepared melt suspension or emulsion additionally from emulsifiers the group of fatty alcohols, fatty acids, polyglycerol esters and / or polyoxyalkylene loxanes in amounts of 1 to 20% by weight, preferably 2 to 15% by weight, and be particularly preferably from 2.5 to 10% by weight, based in each case on the melt suspension or emulsion. 21. The method according to any one of claims 1 to 20, characterized in that the method step c) is carried out at temperatures which are at most 10 ° C., preferably a maximum of 5 ° C and in particular a maximum of 2 ° C above the solidification temperature of the Melt suspension or emulsion. 22. The method according to any one of claims 1 to 21, characterized in that in procedural Step c) the melt suspension or emulsion using a piston metering pump, a pneumatic pump, a peristaltic pump or a gear pump in the Molded body is filled.   23. The method according to any one of claims 1 to 22, characterized in that the Mul Molded body before filling with the melt suspension or emulsion be warmed to improve the adhesion of the cooling melt.