SK10052000A3 - Moulded body containing activating agents, alkali carriers, bleaching agents, enzymes and tensides - Google Patents

Abstract

Die vorliegende Erfindung betrifft Formkörper, welche Builderstoffe, Alkaliträger, Bleichmittel, Enzyme und Tenside enthalten. Besonders leistungsstarke Formkörper mit hoher Lagerstabilität, gutem Duftprofil und definiertem Löslichkeitsprofil werden erhalten, wenn ein Bereich, der nicht mehr als 40 Vol.-% des Formkörpers ausmacht, mehr als 80 Gew.-% des Gesamtgehalts einer im Formkörper enthaltenen Aktivsubstanz I mit einem Bestandteil aus der Gruppe der Chlorbleichmittel und einer schmelzbaren Komponente zur Löslichkeitskontrolle aus der Gruppe der Tenside, der Paraffine, der Mikrowachse und der höhermolekularen Polyethylenglycole enthält.

Description

Shaped product containing activating agents, alkalinity sources, bleaching agents, enzymes and surfactants

Technical field

The invention relates to laundry detergent and cleaning detergent moldings, in particular tablets such as dishwashing tablets, detergent tablets, bleach tablets, stain removers tablets or water hardness tablets for domestic use, in particular for machine use, as well as for machine use. a process for making these shaped articles and their use.

BACKGROUND OF THE INVENTION

Laundry and cleaning detergent moldings, especially tablets, have a number of advantages over powder formulations, such as convenient handling, easy dispensing, and low packaging requirements.

However, problems arise because relatively high compression pressures have to be used to compress the powder components in order to achieve sufficient shape stability and fracture resistance. Because of their strong compaction, such tablets often have insufficient storage stability due to sensitive ingredients (bleach, perfume, enzymes, silver preservative, colorants, surfactants), reduced performance (especially when contaminated such as tea, milk, starches) compared to comparable amounts active substance in other forms of existence, in many cases improved protection of sensitive materials to be cleaned and impaired disintegration and dissolution properties when used.

In some prior art patents, some of these problems have already been solved.

Often, however, the consumer cannot be satisfied with the performance benefits described there. Therefore, it is an important problem for the seller of laundry and cleaning detergent moldings to satisfy this consumer.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide high performance, easy to handle laundry detergent or cleaning detergent moldings, in particular dishwashing detergent tablets, laundry detergent tablets, stain removers tablets or water hardness tablets for use in water.

-2Households, especially for machine applications with high storage stability, low packaging costs, good fragrance profile and defined solubility profile, which mainly guarantee high customer satisfaction.

This was surprisingly solved by a shaped article in which the active ingredient (I) was predominantly in a defined space, the space being not more than 40% by volume. shaped article.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides a shaped article comprising activating agents, alkalinity sources, bleaching agents, enzymes, and surfactants, and which in a space not exceeding 40% by volume. % of the molded article contains more than 80 wt. blends of an active ingredient (I) of a bleaching agent from the group of chlorine bleaching agents and a fusible component to control solubility selected from the group of surfactants, paraffins, micro-waxes and high molecular weight polyethylene glycols.

The active ingredient (I) can be a bleach activator, a silver preservative and / or a soil release compound, an enzyme, a surfactant or a solubility control component or mixture in addition to a chlorine-based bleaching agent. However, the active ingredient (I) may also be a mixture of several of these components.

It is particularly preferred that the active ingredient (I) is a mixture of one component or a mixture for controlling solubility and at least one other active ingredient from the group consisting of bleaching agents and / or bleach activator and / or silver preservative and / or soil release compound. and / or an enzyme and / or a surfactant.

The solubility of the active substance compartment (I), the surface and type of compression and the storage stability may also have a decisive influence on the properties of the tablet.

It is preferred in the sense of the present invention that a space with more than 80% by weight, preferably with more than 90% by weight, more preferably with more than 95% by weight. and most preferably, with the total content of existing active ingredient (I), it is surrounded in exactly three spatial directions by other active ingredients of the shaped article.

Within the scope of the present invention, it is also preferred that at least one space with more than 80% by weight, preferably with more than 90% by weight, more preferably with more than 95% by weight. and most preferably it dissolves by more than 5%, preferably by more than 10%, more preferably by more than 25%, with the total active compound (I) present,

Particularly preferably by more than 50% and most preferably by more than 100% faster than the remaining spaces of the molded article.

It is also positive if the space with no more than 40% of the surface, preferably between 5 and 30%, more preferably between 10 and 25%, most preferably between 15 and 20% by volume. The molded article comprises more than 80 wt.%, preferably more than 90 wt.%, more preferably more than 95 wt. and most preferably the total amount of active ingredient (I) present.

The desired effect on the overall result can also be achieved by the weight gain of the active substance compartment (I) when stored under normal household conditions, i. between 15 and 30 ° C and between 5 and 55% air humidity, more preferably 15 and 35% air humidity for 30 days, more preferably 60 days, most preferably 90 days, not more than 50 wt%, preferably not more than 40 wt%. %, preferably not more than 30% by weight, particularly preferably not more than 20% by weight, and extremely preferably not more than 10% by weight. % and most preferably not more than 5 wt.

The desired effect on the overall result can also be achieved by the fact that the loss of the active ingredient (I) of the storage space under normal household conditions, i. between 15 and 30 ° C and between 5 and 55% air humidity, more preferably 15 and 35% air humidity for 30 days, preferably 60 days, more preferably 90 days, not more than 50 wt%, preferably not more than 40 wt%. %, preferably not more than 30 wt.%, particularly preferably not more than 20 wt. % and extremely preferably not more than 10 wt. % and most preferably not more than 5 wt.

The desired effect on the overall result can also be achieved by the absorption maximum of a 1% solution of the tinted space or the tinted component when stored under normal household conditions, i. between 15 and 30 ° C and between 5 and 55% air humidity, more preferably 15 and 35% air humidity for 30 days, preferably 60 days, more preferably 90 days, not more than 100 wavelengths, preferably not more than 50 wavelengths, more preferably not more than 30 wavelengths, particularly preferably not more than 20 wavelengths and extremely preferably not more than 10 wavelengths, and most preferably not more than 5 wavelengths.

Likewise, the molded article according to the invention has a positive effect when a space with more than 80% by weight, preferably with more than 90% by weight, more preferably with more than 95% by weight. and most preferably, with the total amount of active ingredient (I) present, it is surrounded in exactly three spatial directions by other active ingredients of the shaped article.

-4Rozpustnosť

The solubility can be influenced by means of components and / or mixtures to accelerate dissolution (disintegrants) or to retard dissolution.

All disintegrants known in the art can be used as disintegrants. In particular, reference is made to the textbook Rômpp (9th edition, volume 6, page 4440) and Voigt "Lehrbuch der pharmazeutischen Technologie" (6th edition, 1987). Particularly suitable are substances such as starches, cellulose and cellulose derivatives, alginates, dextrans, cross-linked polyvinylpyrrolidones and others; weak acid systems and carbonate-containing compositions, in particular citric acid and tartaric acid in combination with bicarbonate or carbonate, as well as a polyethylene glycol sorbitan fatty acid ester.

International patent application WO-A-96/06156 also discloses that the incorporation of disintegrants into detergent or cleaning tablets may be advantageous. Again, microcrystalline cellulose, sugars such as sorbitol, but also layered silicates, especially fine-grained and swellable layered silicates of the bentonite and smectite type, are mentioned as typical disintegrants. Gas-assisting substances such as citric acid, hydrogen sulphate, bicarbonate, carbonate and percarbonate are also mentioned as possible disintegrants.

European Patent Applications EP-A-0 466 485, EP-A-0 522 766, EPA-0 711 827, EP-A-0 711 828 and EP-A-0 716 144 disclose the manufacture of detergent cleaning tablets, wherein: a compact, particulate material with a particle size between 180 and 2000 µm is used. The resulting tablets may have a homogeneous as well as a heterogeneous structure. According to EP-A-0 522 766, at least the particles containing surfactants and activating additives are coated with a binder / disintegrant solution or dispersion, in particular polyethylene glycol. Other binders / disintegrants are once again described and known disintegrants, for example starches and starch derivatives, commercially marketed cellulose derivatives such as cross-linked and modified cellulose, microcrystalline cellulose fibers, cross-linked polyvinylpyrrolidones, layered silicates, etc. Even weak acids such as citric or tartaric acids, which together with carbonate-containing sources, in contact with water, give rise to the effects of a spring and, as defined by Römpp, belong to the second class of disintegrants, can also be used as a coating material.

In particular, reference is made to DE 197 10 254, which has not been published, which discloses disintegrants having a particle size distribution (screen analysis) that

At most 1% by weight, more preferably less, is in the form of dust fractions, and in total (including any dust fractions present) less than 10% by weight. the disintegrant granulate is less than 0.2 mm. Preferably, at least 90 wt. the disintegrant granulate has a particle size of at least 0.2 mm and at most 3 mm. These disintegrants are particularly suitable for the present invention. Molded detergent products containing disintegrants in granular or optionally co-granular form are also described in German patent application DE 197 09 991 (Stefan Herzog) as well as in international patent application WO 98/40463 (Henkel). These publications also provide details on the production of granular, compacted or cogranular cellulose disintegrants. The particle size of these disintegrants is generally greater than 200 µm, more preferably at least 90% by weight. it has a size of between 300 and 1600 μιτι and in particular at least 90% by weight. between 400 and 1200 pm. The coarse cellulose-based disintegrants described in more detail in the above and cited publications are preferably used as disintegrants in the present invention and commercially available, for example, under the designation Arbocel (R) TF-30-HG from Rettenmaier.

Also suitable are organic acid formulations such as citric acid, optionally a mixture of citric acid / bicarbonate and / or cellulose and cellulose derivatives. If a disintegrant is present in the molded article, then the dissolution time of the total molded article is preferably less than the main wash process of a conventional dishwasher, i.e. less than 40 minutes, preferably less than 30 minutes, more preferably less than 20 minutes, and particularly preferably less than 10 minutes .

As a material for retarding dissolution, paraffins and / or microwaxes and / or high molecular weight polyethylene glycols, which are widely described in the prior art, are generally customary. Particularly suitable for the present application is the use of mixtures as mentioned in DE 197 27 073, which has not been published so far, and the teachings of which are hereby incorporated by reference.

If a dissolution retardant is present, in a more preferred embodiment, the dissolution time of the total molded article in 20 ° C cold water is longer than the prewash process in a conventional dishwasher, i.e. longer than 5 minutes, especially longer than 10 minutes.

-6General shapes

All possible three-dimensional bodies are suitable for the spatial shapes of the molded articles, inter alia in the prior art patents and in the standard literature (e.g. Riedel " Die Tablette ") but also in the prior art patents. The space in which the active ingredient (I) is contained is likewise not bound to any specific spatial shape. However, for practical reasons, the preferred area in each spatial direction is greater than 5 mm.

Specific embodiments

In a more preferred embodiment of the invention, homogeneous or heterogeneous shaped articles of a known construction method are prepared.

These include, in particular, cylindrical tablets, which tablets preferably have a diameter of 15 to 60 mm, in particular 30 +/- 10 mm. The height of these tablets is preferably 5 to 30 mm, and in particular 15 to 28 mm. Molded articles having a diameter of 32, 33, 34, 35, 36, 37, 38 and 39 mm respectively have proven to be particularly advantageous. The height was 24, 25, 26, 27 and 28 mm in special embodiments.

However, it is also possible to use square, rectangular, trapezoidal, oval and irregularly shaped bases. The edge length is preferably from 15 to 60 mm, in particular 30 +/- 10 mm.

The weight of the individual shaped articles, in particular tablets, is preferably from 15 to 60 g and in particular from 20 to 40 g per shaped article or tablet; the density of the fabric of the molded article or of the tablet usually has values above 1 kg / dm ³ , in particular from 1.1 to 1.4 kg / dm ³ .

Depending on the type of use, the extent of water hardness or contamination, it is possible to use 1 or more, for example 2 to 4 shaped products, in particular tablets. Other shaped articles according to the invention may also have a smaller diameter or dimensions, for example 10 mm.

Homogeneous shaped articles are understood to be those in which the active substances of the shaped article are dispersed homogeneously to the active substance space (I) in such a way that the different active substances cannot be distinguished by the naked eye. Of course, the granulometric composition of the solids used can still be distinguished. In a more preferred embodiment of the invention there is only one space (phase) in addition to the active substance compartment (I).

By heterogeneous molded articles is meant correspondingly those which do not have a homogeneous distribution of the active substances contained in addition to the active substance (I). The heterogeneous shaped articles can be produced in a simple case, for example, in that the different active substances have different colors and / or carry different fragrances.

Another case, which according to the invention belongs to non-uniform (heterogeneous) shaped articles, comprises a molding in which a shaped article is pressed which, in addition to the active substance compartment (I), contains several layers (at least 2 layers). For example, it is possible for these different layers to have different disintegration and dissolution rates and / or to contain different active substances. This may advantageously result in the application properties of the shaped article. If, for example, active substances which have a negative effect on each other are present in the molded article, they can be separated. If a defined order of cleaning conditions is to be created in the machine, it is possible to integrate the component (or multiple components) in one (or more) faster disintegrating and / or faster soluble layer and incorporate the other components in a slower disintegrating layer so that the component can interact with in advance or already react when another passes into solution.

A more preferred embodiment of the invention is that in addition to the active substance compartment (I), two further phases are present. It is particularly preferred that the volume ratios of the two other phases are between 10: 1 and 1:10, more preferably between 5: 1 and 1: 5, most preferably between 2: 1 and 1: 2.

Another particularly preferred embodiment is characterized in that three or more additional phases are present.

The structure of the layers of the molded article may be stacked, the process of dissolving the inner layers at the edge of the molded article even when the outer layers are not yet completely dissolved or disintegrated; however, it is also possible to achieve complete and / or partial wrapping of the inner layers by means of outer layers, which leads to the prevention and / or retardation of premature dissolution of the components of the inner layer.

In a further preferred embodiment of the invention, the tablet consists of at least three layers, i.e. two outer and at least one inner layer, wherein at least one of the inner layers comprises a peroxide bleaching agent, whereas in a stacked tablet both outer layers and a coated tablet do not contain peroxide bleaching agent. It is also possible in

The peroxide bleaching agent and any bleach activators or bleach catalysts and / or enzymes present may be spatially separated from each other / molded article. Such shapes have the advantage that no undesired mutual effects are to be feared in the molded article according to the invention.

Another advantageous and advantageous embodiment of the invention is that one or more bleaching components, in particular the chlorine components, are not packaged together in one phase with the perfume components. A further advantageous and advantageous embodiment of the invention is that the silver protection components are not packaged together with the bleaching components. Another advantageous and advantageous embodiment of the invention is that at least one of the components for controlling solubility is packaged together with a bleach activator. Another advantageous and advantageous embodiment of the invention is that at least one of the components for controlling solubility is packaged together with enzymes. Another advantageous and advantageous embodiment of the invention is that at least one of the components for controlling solubility is packaged together with bleaching agents. A further advantageous and advantageous embodiment of the invention is that at least one of the components for controlling solubility is packaged together with the silver protecting component. Another advantageous and advantageous embodiment of the invention is that at least one of the components for controlling solubility is packaged together with at least 50% by weight, preferably more than 70% by weight, more preferably more than 90% by weight. or a total surfactant mixture.

The preparation of the composition according to the invention is carried out by a conventional molding process.

In some embodiments, it has proven to be particularly advantageous to fill the active ingredient compartment (I) in the form of a liquid (generally with a solution and / or melt) or at elevated temperatures to a ready recess in the surrounding active ingredients. generally by drying and / or cooling). A viscosity of more than 1500 mPas, preferably greater than 2000 mPas, more preferably between 2000 and 15000 mPas, particularly preferably between 2500 and 7000 mPas and particularly preferably between 3000 and 4000 mPas, has proven to be suitable. A method for producing such molded articles filled with a melt dispersion or melt emulsion is disclosed in German patent application DE 198 31 704.2 (Henkel KGaA). A method for producing coated particles, in particular coated particles of chlorine bleaching agents, is also described in German patent application DE 197 27

-9073.5 (Henkel KGaA). In accordance with the teachings of this document, the coated particles produced can be pressed or pressed directly onto or into shaped articles, or melted and filled into a depression.

The combination of the active compound (I) with fusible carriers has proved to be particularly effective. These include in principle all substances having a freezing point at room temperature or, in particular, at a temperature higher than room temperature.

Particularly suitable for the purposes of the present invention are nonionic surfactants (Dehypon (R) LT 104, Dehypon (R) LS 54, Dehydol (R) LS 30, Lutensol (R) AT 80), polyethylene glycols of different molecular weights (PEG 400, 12000), soaps (Lorol (R) C16). , stearates (Cutina® GMS) but also concentrated sodium hydroxide solution and fusible salts such as sodium carbonate decahydrate. The advantages and disadvantages of the individual active ingredients can be understood by one skilled in the art by experimentation. Waxes are particularly preferred as fusible components within the scope of the present invention. 'Waxes' means a series of natural or synthetically derived substances which, as a rule, melt without decomposition at temperatures above 40 ° C and already at a temperature slightly higher than the melting point, they have a low viscosity and are not filiform. They have a consistency and solubility strongly dependent on temperature.

According to their origin, the waxes are divided into three groups, 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 wax, sugar cane wax, ouricury wax or montan wax, animal waxes such as beeswax, shellac wax, shellac wax, shellac wax, shellac wax, shellac wax. sperm, lanolin or coccyx fat, mineral waxes such as ceresin or ozokerite (natural wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

Chemically modified waxes include, for example, hard waxes such as montanester waxes, solvolves, or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes.

Also within the scope of the present invention, waxes include, for example, so-called wax alcohols. Wax alcohols are high molecular weight water-insoluble fatty alcohols having more than 28 to 40 carbon atoms. Wax alcohols occur, for example, in the form of wax esters of high molecular weight fatty acids (wax acids) as a major component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol) or melisyl alcohol. meltable

The component may optionally also contain sheep wool wax alcohols, which are understood to mean triterpene and steroid alcohols, for example lanolin. Also at least partially as the melt component useful in the present invention are fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or sparingly soluble polyalkylene glycol compounds.

Preferably, the fusible components comprise predominantly paraffin wax. That is, at least 50 wt. more preferably the paraffin wax. Particularly suitable are paraffin wax contents of about 60% by weight, about 70% by weight. or about 80 wt.%, with even greater proportions, for example, greater than 90 wt. are particularly preferred. In a particularly preferred embodiment of the invention, the fusible component consists exclusively of paraffin wax.

Paraffin waxes have the advantage over other natural waxes of the present invention that the alkaline cleaning agent does not undergo hydrolysis of the wax (as would be expected, for example, with wax esters), since the paraffin wax does not contain any groups capable of hydrolysis.

Paraffin waxes consist mainly of alkanes as well as small proportions of iso- and cycloalkanes. The paraffin used according to the invention preferably contains essentially no constituents having a melting point above 70 ° C, particularly preferably above 60 ° C. The proportions of high melting alkanes in the paraffin can leave unwanted residues on the surfaces to be cleaned or the objects to be cleaned when the melting point is not reached in the detergent bath. As a rule, such cleaning residues lead to the uneven appearance of the surfaces to be cleaned and should therefore be avoided. The packaging of the invention preferably comprises at least one paraffin wax having a melting point of from about 57 ° C to about 60 ° C.

It is preferred to use as high a content of alkanes, isoalkanes and cycloalkanes as possible in the paraffin wax used, which are solid at ambient temperature (generally from 10 to 30 ° C). The more solid wax components the wax contains at room temperature, the more suitable it is for use in the present invention. As the proportion of solid wax components increases, the load-bearing capacity of the coating against impacts or friction with other surfaces increases, leading to longer protection of the coated particles. High proportions of oils or liquid wax components can cause the packaging to weaken, thereby opening pores and particles containing fusible components initially exposed to the above environmental influences.

At unusually low temperatures, for example below 0 ° C, the solidified melt component may break upon impact or friction. In order to improve the stability at such low temperatures, it is possible to admix the melt component or the additive. Suitable additives must be capable of being completely mixed with the melted wax, must not significantly change the melting range of the packaging, must improve the elasticity of the solidified fusible component at low temperatures, must not increase the permeability of the solidified fusible component to water or moisture in general, and must not increase the melt viscosity to make processing worse or impossible. Suitable additives which reduce the brittleness of a substantially paraffin-containing coating at low temperatures are, for example, EVA copolymers, hydrogenated resin methyl esters, polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.

The fusible components may contain, in addition to paraffin, as the main component, one or more of the above-mentioned waxes or waxy substances. In principle, the coating composition should be formed such that the packaging is at least to a large extent water-insoluble. The water solubility at about 30 ° C should not exceed about 10 mg / l and more preferably less than 5 mg / l.

Particularly suitable for the present application is the use of mixtures as described in the unpublished DE 197 27 073, the teachings of which are hereby expressly incorporated herein.

In other embodiments, portions of the molded article and / or molded article component are treated by microwave irradiation to positively affect strength, moisture content, and solubility.

However, simple compression of the components is also possible. In addition to powders and granules, it is also possible to use micro-tablets and shaped articles with smaller dimensions than the finished shaped article.

Active substances

Particularly active substances (I) which are additionally used in the context of the invention are substances which prevent re-contamination of surfaces and / or facilitate the dissolution of the contamination (so-called soil-release compounds) after a single use.

The soil release compounds used according to the invention include all known compounds. Particularly suitable are cationic polymers, such as are known from the following publications:

12V EP-A-0 167 382, EP-A-0 342 997 as well as DE-OS-26 16 404 contain cationic polymers in the cleaning compositions to achieve surface cleaning as streak-free as possible.

EP-A-0 167 382 discloses liquid detergent compositions which may contain cationic polymers as a thickening agent. Hydroxypropyltrimethylammonium guar, copolymers of aminoethyl methacrylate and acrylamide as well as copolymers of dimethyldialylammonium chloride and acrylamide are described as particularly suitable cationic polymers.

EP-A-0 342 997 discloses universal cleaners which may contain cationic polymers, in particular polymers having imine groups are used.

DE-OS-26 16 404 describes glass cleaners containing cationic cellulose derivatives. The addition of cationic cellulose derivatives in the compositions will improve the water run-off, thereby achieving streak-free glass cleaning.

EP-A-0 467 472 discloses, for example, hard surface cleaners which contain cationic homo- and / or copolymers as soil release polymers. These polymers have quaternized ammonium alkyl methacrylate groups as monomer unit. These compounds are used for surface treatment which makes it easier to release contamination during the next cleaning process.

Particularly preferred as soil release compounds are cationic polymers selected from cationic copolymers of copolymers such as trialkylammonium alkyl (meth) acrylate or -acrylamide; dialkyldialyldiammonium salts; polymer analogs of the reaction products of ammonium side-group ethers or esters of polysaccharides, in particular guar, cellulose and starch derivatives; polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides with quaternary side groups.

Unusually suitable within the scope of this application are also natural polyuronic acids and related substances, as well as polyampholytes and hydrophobized polyampholytes, or mixtures thereof.

The detergent compositions of the present invention may contain from 0 to 5 wt.% To enhance the performance of the detergent composition or to guarantee cleaning performance of the same quality under milder conditions. enzyme relative to the total preparation. The most commonly used enzymes include lipases, amylases, cellulases and proteases. Preferred proteases are BLAP® 140 from Biozym, Optimase®-M440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal® CX and Maxapem® or

-13Esperase® from Gist Brocades or Savinase® from Novo. Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk are particularly suitable cellulases and lipases. Duramyl® and Termamyl® 60 T, and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades have particular applications as amylases. The use of other enzymes is also possible.

Other active substances

Particularly active compounds used in the present invention are oxygen bleaching agents, more preferably alkali metal perborates and their hydrates and alkali metal percarbonates, with sodium perborate such as mono- or tetrahydrate or sodium percarbonate and sodium percarbonate and its peroxygenate are preferred. hydrates. Peroxosulphates are also applicable.

However, organic peroxyacids are also typical oxygen bleaching agents. Preferred organic peroxyacids include, in particular, the excellent active phthalimidoperoxycaproic acid, but all other peroxyacids known in principle are also applicable.

Particular active substances which are used in the present invention are bleach activators. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as those of the anhydride, ester, imide and acylated imidazoles or oximes class. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and ISA anhydride.

Bleach activators which may be used are compounds which, under peroxohydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acids. Suitable are those having O- and / or Nacyl groups of the indicated number of carbon atoms and / or optionally substituted benzoyl groups. Preferred are multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetyl glycoluril (TAGU) , N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially anhydride

-14 phthalic acids, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate,

2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol, or mixtures thereof (SORMAN) described in European patent application EP 0 525 239, acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated or alkyl-alkylated glucamine and gluconolactone, and / or Nacylated lactams, benzoyl caprolactam known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498. The hydrophilic substituted acyl acetals known from the German patent application DE 196 16 769 and the acyl lactams described in the German patent application DE 196 16 770 as well as the international patent application WO 95/14075 are also advantageously applicable. It is also possible to use a combination of conventional bleach activators known from German patent application DE 44 43 177. Such bleach activators are included in the conventional quantitative range, preferably in amounts of from 1 wt. % to 10 wt.%, especially from 2 wt. up to 8 wt. relative to the total composition.

In addition to or instead of the conventional bleach activators mentioned above, sulfonimines known from European patents EP 0 446 982 and EP 0 453 003 and / or for bleaching stronger transition metal salts or transition metal complexes may also be present as so-called bleach catalysts. Suitable transition metal compounds include, in particular, manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 195 29 905 and their N-analogous compounds known from German patent application DE 196 20 267, carbonyl complexes of manganese, iron , cobalt, ruthenium or molybdenum known from German patent application DE 195 36 082, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands described in German patent application DE 196 05 688 to ammonium acetate complexes , iron, copper and ruthenium known from German patent application DE 196 20 411, manganese, copper and cobalt complexes described in German patent application DE 44 16 438, cobalt complexes described in European patent application EP 0 272 030, manganese complexes known from European patent application EP 0 693 550, manganese, iron, cob alta and copper known from European patent EP 0 392 592 and / or manganese complexes described in U.S. Pat

-European patent EP 0 443 651 or in European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519. Combinations of bleach activators and bleach catalysts based on transition metals are known, for example, from German patent application DE 196 13 103 and from international patent application WO 95/27775. Preference is given to using bleach activators from the group of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate, MMA, more preferably in amounts up to 10% by weight, in particular 0.1% by weight. % to 8% by weight, in particular from 2% to 8% by weight. % and in particular from 2% to 6% by weight. relative to the total composition.

Bleach-enhanced transition metal complexes, in particular with central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, more preferably selected from the group of salts and / or manganese and / or cobalt complexes, particularly preferably (ammonium) complexes cobalt (acetate) cobalt complexes, (carbonyl) cobalt complexes, cobalt or manganese chlorides, manganese sulfate are used in conventional amounts, more preferably up to 5% by weight, in particular from 0.0025% by weight. % to 1 wt. % and most preferably from 0.01 wt. % to 0.25 wt. relative to the total device. In special cases, more bleach activators may be used.

The dishwashing compositions according to the invention may contain corrosion inhibitors as an active substance for the protection of articles or machines to be washed, with silver protection agents being of particular importance in the field of machine dishwashing. Materials known from the prior art, such as those described in DE 43 25 922, DE 41 28 672 or DE 43 38 724, are usable. In particular, silver preservatives selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles may be used in particular. and transition metal salts or complexes. Particularly preferred for use are benzotriazole and / or alkylaminotriazole. According to the abovementioned documents, it is possible in particular to use oxygen-containing and nitrogen-containing redoxactive compounds, such as divalent and trivalent phenols, for example hydroquinone, pyrocatechin, hydroxyhydroquinone, gallic acid, floroglucine, pyrogalol or derivatives of these classes of compounds. Salts and complex inorganic compounds, such as Mn, Ti, Zr, Hf, V, Co and Ce metal salts, will often find use. Preferred are the transition metal salts selected from the group of salts and / or manganese and / or cobalt complexes, with the (ammonium) cobalt complexes being particularly preferred,

- 16 (acetate) cobalt complexes, (carbonyl) cobalt complexes, cobalt or manganese chlorides and manganese sulphate. It is also possible to use zinc compounds to prevent corrosion on washed objects.

In the shaped articles according to the invention, all the active substances (I) described above can also assume the function of other active substances, provided that the condition of the range of other active substances is fulfilled according to the invention.

Water-soluble and water-insoluble builders can be used in the detergent compositions according to the invention, in particular for the binding of calcium and magnesium. Water-soluble builders are preferred, since they tend to have less tendency to form insoluble residues on the series and hard surfaces. Conventional activating additives which may be present in an amount of between 10 and 90 wt. based on the overall formulation are low molecular weight polycarboxylic acids and their salts, homopolymeric and copolymeric polycarboxylic acids and their salts, carbonates, phosphates and silicates. Water-insoluble activating agents include zeolites which can also be used, as well as mixtures of the aforementioned activating agents.

Preference is given to the use of trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate activating agents from the class of disilicates and / or metasilicates.

Alkali sources may be present as additional components. Alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, alkali silicates, alkali metasilicates and mixtures of the foregoing are preferred as alkalinity sources, with alkali carbonates, especially sodium carbonate, sodium bicarbonate or sesquicarbonate, being preferred for use in the present invention. sodium.

Particularly preferred is an activating system comprising a mixture of tripolyphosphate and sodium carbonate.

Equally particularly preferred is an activation system comprising a mixture of sodium tripolyphosphate and sodium carbonate and sodium di-silicate.

Suitable surfactants are, in principle, all surfactants. Preferred are nonionic surfactants, and in particular weakly foaming nonionic surfactants, but other weakly foaming surfactants are also contemplated. Particularly preferred are alkoxylated

- 17alcohols, in particular ethoxylated and / or propoxylated, alkyl polyglycosides and alkyl polyglucamides.

In this case, the expert understands Alkoxylated alcohols are generally the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, long-chain alcohols (C ₈ to Cw, preferably between C 12 and C _16, such as Cn, C12, C13 , C14-, C15-, Cw-, C17- and _C18- alcohols). Depending on the reaction conditions, n moles of ethylene oxide and one mole of alcohol give a complex mixture of addition products with different degrees of ethoxylation, as a rule. Another embodiment consists in using a mixture of alkylene oxides, more preferably a mixture of ethylene oxide and propylene oxide. By the final etherification of short-chain alkyl groups, in particular butyl groups, it is also possible to obtain, as a class of substances, "closed" alcohol ethoxylates which can also be used according to the invention. Highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates are particularly preferred for the purposes of the present invention.

Alkyl polyglycosides are surfactants obtainable by the reaction of sugars and alcohols according to the corresponding preparative organic chemistry procedure, whereby a production method produces a mixture of monoalkylated, oligomeric or polymeric sugars. Preferred alkyl polyglycosides may be alkyl polyglucosides, with a particularly preferred alcohol being a long chain fatty alcohol or a mixture of long chain fatty alcohols, and the degree of sugar oligomerization is between 1 and 10.

Polyhydroxy fatty acid amides (glucamides) are the acylated reaction products of reductive amination of sugar (glucose) with ammonia, and long chain fatty acids, long chain fatty acid esters and long chain fatty acid chlorides are generally used as acylating agents. In this case, secondary amides are formed when methylamine or ethylamine is used instead of ammonia, as described, for example, in S vFW-Journal, 119, (1993), 794-808. Preferably, carbon chain lengths from C 6 to C 12 in the fatty acid residue are used.

The spaces of the molded article may be colored. It is particularly advantageous here that one or more or all of the spaces of the molded product are colored differently. In a special embodiment of the shaped article, this color is red. In another special embodiment of the shaped article, the color is green. In another special embodiment of the shaped article, the color is

-18žltá. In another special embodiment of the shaped article, the color is a mixture of different colors.

The storage stability of the molded article is particularly important. According to the invention, it is particularly advantageous here that the weight gain of the active substance compartment (I) when stored under normal household conditions, i. between 15 and 30 ° C and between 5 and 55% air humidity, more preferably 15 and 35% air humidity for 30 days, preferably 60 days, more preferably 90 days, not more than 50 wt%, particularly preferably not more than 40 wt% %, in particular not more than 30% by weight, particularly preferably not more than 20% by weight. % and extremely preferably not more than 10 wt. % and most preferably not more than 5 wt.

In addition, it is particularly advantageous according to the invention if the loss of the active ingredient in the active ingredient (I) is stored under normal household conditions, i.e. in the case of storage. between 15 and 30 ° C and between 5 and 55% air humidity, more preferably 15 and 35% air humidity for 30 days, preferably 60 days, more preferably 90 days, not more than 50 wt%, preferably not more than 40 wt%. %, preferably not more than 30 wt.%, particularly preferably not more than 20 wt. % and extremely preferably not more than 10 wt. % and most preferably not more than 5 wt.

In this connection, it is particularly advantageous according to the invention that the absorption maximum of a 1% solution of the colored space or the colored component during storage under normal household conditions, i.e. between 15 and 30 ° C and between 5 and 55% air humidity, more preferably 15 and 35% air humidity for 30 days, preferably 60 days, more preferably 90 days, not more than 100 wavelengths, preferably not more than 50 wavelengths, more preferably not more than 30 wavelengths, particularly preferably not more than 20 wavelengths and extremely preferably not more than 10 wavelengths, and most preferably not more than 5 wavelengths.

DETAILED DESCRIPTION OF THE INVENTION

The following recipes and molded moldings were mixed. The active substances indicated in brackets are an example for the class of substances but may be replaced by other substances listed in the application. Framework formulations represent preferred ranges of the invention.

When measuring efficacy, the active ingredient (I) selected was always transferred to the space according to the invention. Before carrying out the determination, it was reduced or omitted completely in another space (s) according to the invention.

Possible frame formulation (Ra) and comparative formulation (Va) (data are in% by weight):

Active substance ra Ra1 VA2 VA3 VA4 VA5 VA6 Ra7 Phosphate (tripolyphosphate sodium) 30-60 54.8 56.4 30.5 43 48 48 47 sodium carbonate 5-25 15.9 13.2 21.5 7 20 12 24 disodium silicate 0-40 7.3 7.5 33.7 20 3 14 Polymer (Sokalan CP5) 0-10 2.2 2.2 1 5 sodium metasilicate 0-10 1.8 0 sodium bicarbonate 0-10 1 3 - bleach (trichloroisocyanurate) acid) 2-20 11.1 9.0 6.7 15 10 13 9 bleach activator (TAED) (Co-pentaamoniakát-Cl) 0-5 2.1 3 2 1.5 enzyme (amylase) (Duramyl 60T) 0-5 2.0 2.0 0.7 3 3 3 2.5 enzyme (protease) (Blap 200 WITH) 0-5 1.8 1.8 1.0 2 2 3 2.5 phosphonate or acid phosphonic 0-5 0.9 0.9 2 1.5 nonionic surfactant (Dehypon LS 54) 0-5 2.0 2.0 2.0 2 4 3 1.5 silver protection (Benzotriazole) 0-3 0.3 0.3 0 0.3 0.2 0.5 tableting assistance (Polyethylene glycol) 0-10 6 paraffin (m.p. 53 ° C) 0-10 2.0 1.0 3 perfume 0-1 0.2 0.2 0.2 1 0.4 1 0.5 coloring 0-4 1.4 1.3 1.4 0.7 0.4 1.5

The active ingredient system of the above-mentioned framework formulation can also be formulated as follows (all other active ingredients as in a).

Active substance rb Rb1 VB2 VB3 vb4 VB5 VB6 Rb7 Phosphate (tripolyphosphate sodium) 30-60 59 56 53 48 48 48 47 carbonate (sodium carbonate) 5-25 21.2 20.3 22.7 17 20 16 24 Polymer (Sokalan CP5) 0-10 2 10 5 4 5 sodium metasilicate 0-10 1.8 sodium bicarbonate 0-10 1 3

(% By weight) may also be used as the frame formulation (R) for the present application:

Active substance rc VC1 Rc2 VC3 vc4 phosphate (sodium tripolyphosphate) 15-35 30 21 35 40 carbonate (sodium carbonate) 25-55 39 50 40 35 sodium bicarbonate 10-20 14 19 15 12 Polymer (Sokalan CP5) 0-10 3 0 disodium silicate 0-10 disodium silicate 0-10 0 0 0 5 bleach (trichloroisocyanuric acid) 2-10 7 8 5 6 bleach activator (TAED) 0-5 1 0 1 0 enzyme (amylase) (Duramyl 60T) 0,4-2 1 0.5 0.5 0.5 enzyme (protease) (Blap 200 S) 0,4-2 1 0.5 0.5 0.5 phosphonate or phosphonic acid 0-5 0 0 0 0 nonionic surfactant (Dehypon LS 54) 0-5 2 1 1 1 silver protection (benzotriazole) 0-3 0.5 0 0.3 0 paraffin (m.p. 53 ° C) 0-10 0 0 0 perfume 0-1 0 0 0.7 0 coloring 0-4 0.5 0 1 0

The following may also be used as a frame formulation (R) for the present application (% by weight):

Active substance rd Rd1 Rd2 Very good 3 Very good 4 trisodium citrate 20-55 44 34 44 44 sodium bicarbonate 5-35 24 9 34 20 carbonate (sodium carbonate) 0-10 7 Polymer (Sokalan CP5) 0-10 6 disodium silicate 0-25 20 bleach (trichloroisocyanuric acid) 0-22 12 16 17 20 bleach activator (TAED) 0-25 1 enzyme (amylase) (Duramyl 60T) 0,4-5 2.5 3 1 5 enzyme (protease) (Blap 200 S) 0,4-5 2 3 1 5 phosphonate or phosphonic acid 0-5 1.5 2.3 2 nonionic surfactant (Dehypon LS 54) 0-5 2.5 1.7 2 1 silver protection (benzotriazole) 0-3 0.5 0.5 paraffin (m.p. 53 ° C) 0-10 3 1.5 perfume 0-1 0.9 0.5 1 1 coloring 0-4 0.1 1.5 2

(% By weight) may also be used as the frame formulation (R) for the present application:

Active substance re Re1 Re2 ve3 Re4 citrate (trisodium citrate) 20-55 32 36 38 24 phosphate (trisodium polyphosphate) 20-55 26 23 24 24 carbonate (sodium carbonate) 1-15 11 10 11 15 Polymer (Sokalan CP5) 0-10 5 1.5 6 silicate (sodium silicate) 0-25 3 6 bleach (trichloroisocyanuric acid) 2-20 16.5 3 12 12 bleach activator (TAED) 0-5 5 2 enzyme (amylase) (Duramyl 60T) 0-5 5 3 2 enzyme (protease) (Blap 200 S) 0-5 5 0.5 2 phosphonate or phosphonic acid 0-5 2 2 2

tableting aid (polyethylene glycol) 0-10 6 4 5 0.8 nonionic surfactant (Dehypon LS 54) 0-5 2.5 2.8 2 silver protection (benzotriazole) 0-3 0.2 0.2 paraffin (m.p. 53 ° C) 0-10 perfume 0-1 1 1 1 coloring 0-4 0 1 1

(% By weight) may also be used as the frame formulation (R) for the present application:

Active substance Rf Rf1 VF2 Rf3 VF4 phosphate (trisodium polyphosphate) 40-60 49 49 49 50 carbonate (sodium carbonate) 0-20 17 19 5 Polymer (Sokalan CP5) 0-15 2 4 1 6 silicate (sodium silicate) 0-30 24 6 5 10 bleach (trichloroisocyanuric acid) 0-15 11.5 8 13 8 bleach activator (TAED) 0-5 2 2 enzyme (amylase) (Duramyl 60T) 0-5 2 2 1.5 2.5 enzyme (protease) (Blap 200 S) 0-5 3.9 2 1.5 2.5 phosphonate or phosphonic acid 0-8 0.8 1 1 2 tableting aid (polyethylene glycol) 0-10 0.2 4 3.7 5 nonionic surfactant (Dehypon LS 54) 0-8 1.5 2 4 3 silver protection (benzotriazole) 0-5 0.1 0.5 0.3 0.5 perfume 0-2 1 0.5 0.5 0.5 coloring 0-4 3 2 0.5 1

As a frame formulation (R) for the present application, the following may also be true (data in% by weight):

The following test formula (V) was used:

Active substance rg Rg1 Vg2 Rg3 VG4 phosphate (sodium tripolyphosphate) 30-60 55.7 59.6 46.5 47 disodium silicate 5-40 22.3 17.5 39.2 24 Polymer (Sokalan CP5) 0-10 2.2 2.2 5

sodium metasilicate 0-10 1.8 sodium bicarbonate 0-10 bleach (trichloroisocyanuric acid) 2-20 11.1 10 6.7 10 bleach activator (Co-catalyst) 0-2 1.1 0.5 enzyme (amylase) (Duramyl 60T) 0-5 2.0 2.0 0.7 2.5 enzyme (protease) (Blap 200 S) 0-5 1.8 1.8 1.0 2.5 phosphonate or phosphonic acid 0-5 0.9 0.9 1.5 nonionic surfactant (Dehypon LS 54) 0-5 2.0 2.0 2.0 1.5 silver protection (benzotriazole) 0-3 0.3 0.3 0 0.5 tableting aid (polyethylene glycol) 0-10 paraffin (m.p. 53 ° C) 0-10 2.0 1.0 3 perfume 0-1 0.2 0.2 0.2 0.5 coloring 0-4 1.4 1.3 1.4 1.5

As a frame formulation (R) for the present application, the following may also be true (data in% by weight):

The following test formula (V) was used:

Active substance rh Vh1 VH2 VH3 VH4 Rh5 VH6 VH7 Phosphate (tripolyphosphate sodium) 30-60 40 40 40 45 45 50 35 sodium metasilicate (5- hydrate) 5-45 45 10 40 10 30 20 35 sodium metasilicate (0- hydrate) 5-40 10 10 8 10 8 5 10 disodium silicate 0-40 0 30 0 15 10 5 0 paraffin oil 0-10 4 5 5 5 6 5 0 - bleach (acid trichloroisocyanuric) 0,5-10 1 2 2 3 1 5 5 enzyme (amylase) (Duramyl 60T) 0-5 1 2 2 2 enzyme (protease) (Blap 200 WITH) 0-5 1 2 2 2

nonionic surfactant (Dehypon LS 54) 0-5 2 2 2 2 3 tableting assistance (Polyethylene glycol) 0-10 1 4 2 4 perfume 0-1 0.3 0.3 1 1 0.5 coloring 0-4 0.7 0.7 1 1 2.5

Another frame formulation (R) (% by weight) and test formulation (V) were tested:

Active substance Ri1 Vi1 Vi2 VI3 sodium carbonate 35-55 43.5 45 55 sodium bicarbonate 15-35 15 25 34 Polymer (Sokalan CP5) 3-10 5 3 0 sodium metasilicate 0-10 3 2 0 bleach (trichloroisocyanuric acid) 5-12 7 10 8 bleach activator (TAED) 0-5 2 enzyme (amylase) (Duramyl 60T) 0,4-2 1 1 0.5 enzyme (protease) (Blap 200 S) 0,4-2 1 1 0.5 phosphonate or phosphonic acid 0-5 0 2 0 nonionic surfactant (Dehypon LS 54) 0-5 1 2 1 tableting aid (polyethylene glycol) 0-5 3 silver protection (benzotriazole) 0-3 0.5 1 0 paraffin (m.p. 53 ° C) 0-10 0 2 0 perfume 0-1 0 1 0 coloring 0-4 1 1 1

If a plurality of phases are to be present in a molded article according to the invention, each formulation may also mean components of a single phase, i. the proportions then do not relate as usual to the overall recipe but relate to the composition of the individual phase.

Of course, other active substances customary for machine dishwashing agents (for example, fillers, preservatives, etc.) may also be contained in extremely small amounts in each of the recipes, with the other components having to be varied accordingly.

The manufacture of shaped articles according to the invention utilizes steps known to those skilled in the art in other contexts. A preferred embodiment of the shaped article according to the first claim has a depression in the tablet, the depression comprising a chlorine bleaching active ingredient (I). More preferably, the recess is formed by molding a recess into the shaped article and filling the recess. Pressing can be performed on a Korsch carousel press. In the present case, a Fette tablet press was used. A round tablet form (26 X 36 mm) was chosen and punched 5 mm deep on one side, the base being chosen to fill a volume of 1 ml and the tablet again having a smooth surface.

The liquid mixture of paraffin and the active ingredient (I) was then filled and cooled. This cooling can be supported by conventional instrumentation methods.

As already mentioned, the active ingredient (I) according to the invention in the corresponding formulation that surrounds the filled space was initially reduced in quantity and omitted completely in the present cases and in the surroundings.

In comparative experiments with a homogeneous (not active ingredient (I) according to the invention) and several tablets marketed, the tablets according to the invention prevailed.

The particular properties of the compositions of the invention have been controlled with known compositions, for example, by storage stability. The particular properties of the compositions according to the invention were controlled in comparison with known compositions in the example of tea cleaning. The particular properties of the compositions according to the invention have been controlled in comparison with known compositions in the example of purification of enzyme-relevant contaminants.

In addition, the particular properties of the compositions of the invention were checked in comparison to homogeneous tablets by technically untrained persons under conditions relevant to practice. At the same time, in addition to the dosing and general safety instructions, no influence has been exerted by the surroundings of the persons on handling the appliance in conventional dishwashers. This comparative experiment turned out particularly well. Here, the purification results were judged to be particularly advantageous.

In one experiment, samples according to the Ra Framework formulation were used which contained active chlorine (dichlorocyanurate) as a bleaching component once homogeneously dispersed in the tablet and once according to claim 1, so that active chlorine was separated from the other (especially enzyme) components. Storage stability after two weeks for the homogeneous tablet was considerably worse, so it was not possible to determine

-26 satisfactory cleaning effect for milk and starch contamination. This applies to a perfectly normal bleaching component in compartment (I), which in this case has been deepened. Even more pronounced was the effect of using a mixture of chlorine and paraffin in a standard program at 55 ° C. The cleaning results were better after production. The effect was enhanced during storage. In particular, tea, milk, burnt meat, baked meat, eggs and starch mixtures showed a significantly better cleaning performance than in molded articles without space with the active ingredient (I), with homogeneously dispersed component (I) and with several commercially available cleaners.

The effect could already be observed with paraffins with a melting point of 40 to 44 ° C. The effect is more pronounced for paraffins with a melting point of 46-48 ° C. The cleaning effect of paraffins with a melting point of 57 to 60 ° C is of particular interest.

The results clearly show that the compositions of the invention outweigh conventional dishwashing tablets.

To demonstrate the positive effects, melt dispersions of dichloroisocyanuric acid (DICA) in packaging materials were produced in further examples. Here, an embossed shaped product (weight: 24 g) was produced by pressing with a punch having a pin. The composition (in% by weight based on the masterbatch) and thus the deepened molded article is in the following Table 1:

Table 1: Masterbatch composition (wt.%)

masterbatch sodium carbonate 24.8 sodium tripolyphosphate 62.6 sodium perborate 7.5 tetraacetylethylenediamine 1.1 benzotriazole 0.7 C12-fatty alcohol with 3 EO 1.9 coloring 0.1 enzymes 0.7 perfume 0.1 PEG 400 0.5

By heating the packaging material and mixing the solid active ingredient (DICA), SDE 1 and 2 melt dispersions were produced, the composition (% by weight based on melt) of which is shown in the following table:

SDE 1 SDE 2 Dichloroisocyanuric acid (DICA) * 35 35 paraffin (melting point 46-48 ° C) 65 - paraffin (melting point from 57 to 60 ° C) - 65

* sodium salt: Oxidan® DCN / WP (3V Sigma)

The melt dispersions were filled according to the teachings of German patent application DE 198 31 704.2 into shaped articles and allowed to cool. Before filling, the molded articles had a weight of 24 g and were each filled with 1.3 g of the melt dispersion. The cleaning performance of molded products E1 and E2 filled with melt dispersions SDE 1 and SDE 2 was tested for tea contamination. To this end, according to (1), the tea cups were soiled and cleaned in an ordinary dishwasher:

1) Production of tea pollution

16 L of cold urban water (16 ° d) was briefly brought to boiling in the water preparation kettle. Thereafter, 96 g of black tea in a nylon mesh was allowed to infuse for 5 minutes with the lid closed and the tea was transferred to a dipping apparatus with heating and stirrer. 60 tea cups were immersed 25 times in a one-minute rhythm at 70 ° C in the prepared tea batch. Subsequently, the cups were hung and laid down for drying on a baking tray.

2) Results of experiments

The cleaning performance of the tea contamination agent according to Regulation (1) was visually inspected and evaluated by experts, with a scale of 0 to 10 indicating no cleaning and 10 removal of stains completely. The grades were determined under the wash conditions of 55 ° C / 16 ° d water hardness in the main wash process (i.e. "hard conditions") as well as for 55 ° C / 3 ° d water hardness. Miele G 590 with a universal program was used as a dishwasher.

-28The following table shows the achieved tea cleansing by E1 and E2 compared to the unfilled molded product V

IN E1 E2 mark for 3 ° d 7.0 10,0 10,0 mark for 16 ° d 4.7 8.2 7.6

The results show that the shaped articles E1 and E2 according to the invention outweigh the comparative shaped article V in achieving tea cleansing.

In another example, according to the teachings of German patent application DE 197 27 073.5, dichloroisocyanuric acid (DiCA) was blended in paraffin according to the following recipe:

DICA 35 wt.

% TyloseMH50 15 wt.

% paraffin (from 57 to 60 ° C) 50 wt.

1.3 g of the bleaching composition coated in this manner was poured into a recess of the above-described shaped article and pressed into a solid core. The cleaning performance of the E3 molded article thus produced was 10.0 (3 ° d) and 8.5 (16 ° d) under the above test conditions.

Claims (20)

PATENT CLAIMS 1. A shaped article comprising activating agents, alkalinity sources, bleaching agents, enzymes and surfactants, characterized in that, in a space not exceeding 40% by volume, the molding product comprises a blend. % of the molded article, contains more than 80 wt. blends of an active ingredient (I) of a bleaching agent from the group of chlorine bleaching agents and a fusible component to control solubility selected from the group of surfactants, paraffins, micro-waxes and high molecular weight polyethylene glycols. Molding according to claim 1, characterized in that the space between 1 and 30% by volume, preferably between 2 and 25% by volume, more preferably between 3 and 20% by volume. The molded article comprises more than 90 wt.%, more preferably more than 95 wt. and most preferably the total amount of active ingredient (I) present. Molding according to claim 1, characterized in that the active ingredient (I) is a bleaching agent selected from the group of chlorine-based bleaching agents and another active ingredient selected from the group of bleach activators and / or silver and / or enzyme protecting agents, and and / or components to control solubility and / or other active ingredients. Molded article according to any one of the preceding claims, characterized in that at least one bleaching agent selected from the group of trichlorocyanuric acid, dichloro- or monochlorocyanunates, hypochlorites and other conventional bleaching agents containing chlorine is present. Molded article according to any one of the preceding claims, characterized in that the fusible component is paraffin. Molded article according to claim 5, characterized in that the paraffin has a melting point of greater than 40 to 44 ° C, preferably greater than 46 to 48 ° C, more preferably between 57 and 60 ° C. Molded article according to any one of the preceding claims, characterized in that it further comprises one or more activating ingredients. -30 from the group of gluconates, low molecular weight polycarboxylic acids and their salts, homopolymeric and copolymeric polycarboxylic acids and their salts, carbonates, phosphates and silicates, more preferably pentasodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or hydrogenate / or silicate activating agents of the class of silicates and / or metasilicates. Molded article according to any one of the preceding claims, characterized in that it contains as a builder system a mixture of tripolyphosphate and / or sodium carbonate and / or sodium disilicate. Molded product according to any one of the preceding claims, characterized in that the surfactants are selected from the group of nonionic surfactants, in particular low foaming nonionic surfactants, more preferably alkoxylated and / or propoxylated fatty alcohols, alkylpolyglycosides, alkylpolyglucamides and / or mixtures of the foregoing. A shaped article according to any one of the preceding claims, characterized in that at least one silver preservative selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, more preferably benzotriazole and / or . Molding according to claim 10, characterized in that the transition metal salts are selected from the group of salts and / or complexes of manganese and / or cobalt, preferably (ammonium) cobalt complexes, (acetate) cobalt complexes, (carbonyl) - cobalt complexes, cobalt or manganese chlorides and manganese sulphate. Molding according to any one of the preceding claims, characterized in that the component and / or the components for controlling solubility are selected from the group of paraffins, micro-waxes and high molecular weight polyethylene glycols. -31 Molded article according to any one of claims 1 to 13, characterized in that the component and / or the components for controlling solubility are selected from the group of organic acids, such as citric acid, optionally a mixture of citric acid / bicarbonate and / or cellulose. and cellulose derivatives. Molding according to any one of the preceding claims, characterized in that the bleaching component (s), in particular the chlorine component (s), are not packaged in one phase with the perfume component. A shaped article according to any one of the preceding claims, characterized in that the silver protection component is not packaged together with any of the bleaching components. Molded article according to any one of the preceding claims, characterized in that at least one of the components for controlling solubility is packaged together with a bleach activator. A shaped article according to any one of the preceding claims, characterized in that at least one of the components for controlling solubility is packaged together with enzymes. A shaped article according to any one of the preceding claims, characterized in that at least one of the components for controlling solubility is packaged together with a bleaching agent. A shaped body according to any one of the preceding claims, characterized in that at least one of the components for controlling solubility is packaged together with the silver protecting component. Molding according to any one of the preceding claims, characterized in that at least one of the components for controlling solubility is packaged together with at least 50% by weight, preferably with more than 70% by weight, more preferably with more than 90% by weight. or a total surfactant mixture.