SK9972000A3 - 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 Bleichaktivatoren enthält.

Description

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

Technical field

The invention relates to laundry detergent shaped articles, in particular tablets, for example, dishwashing tablets, laundry detergent tablets, bleach tablets, stain removers tablets or water hardness tablets for domestic use, in particular for machine use, such as as well as the method of making these molded 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 in the compression of the powder components in order to achieve sufficient shape stability and resistance to fracture. 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.

The object of the present invention was therefore the development of efficient, easy-to-handle laundry detergent or cleaning detergent shaped articles, in particular all dishwashing detergent tablets, detergent tablets, stain removers tablets or water hardness tablets for domestic use, in particular for machine use. high storage stability, low packaging costs, good scent profile and defined solubility profile, which ensure above all high customer satisfaction.

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

SUMMARY OF THE INVENTION

Accordingly, the present invention provides a molded article which contains activating agents, alkalinity sources, bleaching agents, enzymes and surfactants and which contains more than 80% by weight in a space not exceeding 40% by volume. active ingredient (I) with a bleach activator component.

In addition to the bleach activator, the active ingredient (I) may additionally contain an oxygen or chlorine bleaching agent, a silver preservative and / or a soil release compound, an enzyme, a surfactant or a solubility control component or mixture. 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 solubility control composition, in addition to a bleach activator and one other active ingredient from a bleaching agent and / or a silver preservative and / or a soil- release and / or enzyme and / or surfactant.

The solubility of the active substance compartment (I), the surface and compression method 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, more preferably with more than 90% by weight, particularly preferably with more than 95% by weight. and very particularly preferably, with the total active ingredient content (I) being 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 there is at least one space with more than 80% by weight, more preferably with more than 90% by weight, particularly preferably with more than 95% by weight. and very particularly preferably with a total active ingredient (I) content which dissolves by more than 5%, more preferably by more than 10%, very particularly preferably by more than 25%, very particularly preferably by more than 50% and in particular by more more than 100% faster than the remaining space and / or the remaining spaces of the shaped article.

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

The desired effect on the overall result can also be achieved by providing a quantitative increase in space with no more than 40% of the surface containing more than 80% by weight. of the active ingredient (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, more preferably 90 days, not more than 50 wt%, more preferably not more than 40 wt% %, very particularly preferably not more than 30% by weight, particularly preferably not more than 20% by weight, and particularly 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, more preferably 60 days, more preferably 90 days, not more than 50 wt%, more preferably not more than 40 wt% very particularly preferably not more than 30% by weight, particularly preferably not more than 20% by weight. % and more 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 and 55% air humidity, more preferably 15 and 35% air humidity for 30 days, more preferably 60 days, particularly preferably 90 days, not more than 100 wavelengths, more preferably not more than 50 wavelengths, very particularly preferred it is not more than 30 wavelengths, particularly preferably not more than 20 wavelengths, and most preferably not more than 10 wavelengths, and most preferably not more than 5 wavelengths.

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

solubility

Solubility can be influenced by components and / or compounds to accelerate the dissolution (disintegrants) or to slow the 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 a bicarbonate or carbonate, and 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, typical disintegrants are microcrystalline cellulose, sugars such as sorbitol, but also layered silicates, in particular fine-grained and swellable layered silicates of the bentonite and smectite type. 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: used a compact, particulate material with a particle size between 180 and 2000 µm. 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 / disintegration aid 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 acid or tartaric acid, which together with carbonate-containing sources, in contact with water, give rise to the effects of a spring and, according to Römpp's definition, belong to the second class of disintegrants, can also be used as a coating material.

In particular, reference is made to unpublished DE 197 10 254 which discloses disintegrants having a particle size distribution (sieve analysis) that a maximum of 1% by weight, preferably less, is in the form of dust fractions and a total (including possibly present dust fractions) less. % as 10 wt. The granulate disintegrant is less than 0.2 mm. Preferably, at least 90 wt. granulate disintegrant 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 WO98 / 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 between 300 and 1600 µm and in particular at least 90 wt. 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 overall molded article is preferably less than the main dishwashing time of a conventional dishwasher, i.e. less than 40 minutes, particularly preferably less than 30 minutes, very particularly preferably less than 20 minutes and particularly preferably less than 10 minutes.

In the context of the present invention, it is particularly preferred that the faster soluble space according to the invention comprises at least one acidifying agent. Suitable acidifiers are, for example, boric acid as well as alkali metal hydrogen sulphates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferred, with citric acid being a particularly preferred acidifying agent. However, other solid mono-, oligo- and polycarboxylic acids are also useful. Again, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group. Also suitable are organic sulfonic acids such as amidosulfonic acid. Commercially available and preferably used in the present invention is Sokalan® DCS (trade mark BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max 50% by weight) and adipic acid (max. 33) % by weight).

Preferred within the scope of the present invention are detergent-shaped articles in which a substance from the group of organic do-, tri- and oligocarboxylic acids or a mixture thereof is used as an acidifying agent in a faster soluble space, the use of citric acid being particularly preferred. Said acidic agents are preferably either as a separate component I or at least as a proportion of this. Accordingly, in the context of the present invention it is preferred that at least 80% by weight, more preferably more than 90% by weight, particularly preferably more than 95% by weight is present. and very particularly preferably the total amount of acidifying agent contained in the molded article in the more rapidly dissolving space.

In addition to the acidifying agent, the more rapidly soluble space in a more preferred embodiment of the present invention may contain other active substances for which the criterion applied to the active substance I, i.e. the active ingredient, is equally advantageous. % at least 80% by weight, more preferably more than 90% by weight, more preferably more than 95% by weight. and very particularly preferably the total amount of the active ingredient contained in the molded article in the faster soluble space. Other active ingredients are, for example, the carbonates and / or bicarbonates mentioned above, the use of which, when used in combination with an acidifying agent in contact with water, produces a gas evolution which further reduces the dissolution time. Such spring systems may be formulated with an excess of acidifying agent to allow acidic prewashing, but other active agents may be incorporated in the more rapidly soluble space so that the spring system releases the other active agents more quickly. If spring systems are used, the dissolution time of the faster dissolution space is preferably even shorter than the above values, i. less than 10 minutes, more preferably less than 5 minutes and especially less than 2 minutes. Such rapidly dissolving compartments can bring considerable benefits to cleaning performance.

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 a mixture as mentioned in DE 197 27 073, which has not yet been published, 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, more preferably longer than 10 minutes. In such cases, the smaller space of the molded article may have slowed dissolution, so that a larger portion of the shaped article is a faster soluble space. By means of such dissolution retardation measures, certain active substances can be released, for example, only in the polishing process, thereby achieving further advantages in cleaning performance.

Instead of the dissolution retarding component, it is also possible to use the dissolution accelerating component. Preferably, such components originate from the group of polyethylene-8-glycols with a molar mass between 1500 and 4000, more preferably between 1500 and 3000.

General embodiments

All possible three-dimensional bodies are suitable for the spatial shapes of the molded article, such as are mentioned 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 shapes.

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) such 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).

Accordingly, heterogeneous shaped articles are understood as meaning 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 belonging to the non-uniform (heterogeneous) shaped articles according to the invention comprises a molding in which a shaped article is pressed which, in addition to the active substance compartment (I), comprises several layers (phases), i.e. 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 result in advantageous 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, particularly preferably between 2: 1 and 1: 2.

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

The layer structure 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 coating of the inner layers by means of outer layers, which leads to the 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 to spatially separate the peroxide bleaching agent and any bleach activators or bleach catalysts and / or enzymes present in the tablet / shaped 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 component. 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 the bleaching components. 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 consists in that at least one of the components for controlling solubility is packaged together with at least 50% by weight, more preferably with more than 70% by weight. % and in particular more than 90 wt. 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 solution and / or melt) or at elevated temperatures to a ready recess in the surrounding active ingredients and allow this space to cure by conventional techniques (very generally by drying and / or cooling). A viscosity of more than 1500 mPas, more preferably greater than 2000 mPas, particularly preferably between 2000 and 15000 mPas, very particularly preferably between 2500 and 7000 mPas, and particularly preferably between 3000 and 4000 mPas, has proved to be suitable.

The combination of the active compound (I) with fusible carriers has proved to be particularly effective. These include, in principle, all substances with 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.

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.

Specific active substances

Particular active ingredients (I) used in the present invention are bleach activators. Known bleach activators are compounds that contain one or more

N- or O-acyl groups, such as those from the class of anhydrides, esters, imides, and acylated imidazoles or oximes. 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-dioxohexahydro-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 z-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethyl acetate , 2,5-diacetoxy-2,5-dihydrofuran, n-methylmorpholinium acetonitrile methyl sulphate (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 N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are 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 hydrophilically 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 above conventional bleach activators, sulfonimines known from European patents EP 0 446 982 and EP 0 453 003 and / or bleach-enhancing transition metal salts or transition metal complexes may also be included as so-called bleach catalysts. Suitable transition metal compounds include, in particular, salen complexes of manganese, iron, cobalt, ruthenium or molybdenum known from German patent application DE 195 29 905 and their N-analogous compounds known from German patent application DE 196 20 267, carbonyl manganese complexes , 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, ammonia cobalt, iron, copper and ruthenium complexes 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 complexes, co and copper or manganese complexes disclosed in 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 transition metal bleach catalysts are known, for example, from German Patent Application DE 196 13 103 and International Patent Application WO 95/27775. Preference is given to the use of bleach activators from the group of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), Nacylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxy (NOB) sulphonate, more preferably in amounts up to 10 wt.%, especially 0.1 wt. % to 8 wt.%, especially from 2 to 8 wt. % and in particular from 2 to 6 wt. relative to the total composition.

Bleach-enhancing 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, more preferably (ammonium) -14 cobalt complexes, (acetate) cobalt complexes, (carbonyl) cobalt complexes, cobalt or manganese chlorides, manganese sulfate are used in conventional amounts, more preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight. % to 1 wt. % and particularly preferably from 0.01 wt. % to 0.25 wt. relative to the total device. In special cases, more bleach activators may be used.

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

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:

In EP-A-0 167 382, EP-A-0 342 997 as well as DE-OS-26 16 404, cationic polymers are added as streak-free as possible in surface-cleaning compositions.

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 flow of water, 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 trialkyl-15 ammonium 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.

From 0 to 5% by weight may be added to the detergent compositions of the present invention to increase 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 Esperase® 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.

Particular active compounds (I) 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 being preferred in the present invention and hydrates thereof. Peroxosulphates are also applicable.

However, organic peroxyacids are also typical oxygen bleaching agents. Preferred organic peroxyacids include, in particular, the highly active phthalimidoperoxocaproic acid, but all other peroxyacids known in principle are also useful.

The dishwashing compositions according to the invention may contain corrosion inhibitors as an active ingredient (I) 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 in the art, such as those described in DE, are useful

In particular, silver preservatives selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes may be used in particular. Particularly preferred for use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine formulations which can greatly reduce the corrosion of silver surfaces. In the chlorine-free cleaners according to the abovementioned documents, in particular organic redoxactive compounds containing oxygen and nitrogen, 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, are also often used. Preferred are transition metal salts selected from the group of salts and / or complexes of manganese and / or cobalt, particularly preferred are (ammonium) cobalt complexes, (acetate) cobalt complexes, (carbonyl) cobalt complexes, cobalt or manganese chlorides, and manganese sulfate. It is also possible to use zinc compounds to prevent corrosion on washed objects.

Other active substances

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 using trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium hydrogencarbonate and / or gluconates and / or silicate activating agents of the class of silicates 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 alcohols, especially ethoxylated and / or propoxylated alcohols, alkyl polyglycosides and alkyl polyglucamides.

The expert understands thereby Alkoxylated alcohols are generally the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention are alcohols, long chain (C 10 to Cie, more preferably between _Ο Ί2 and C _6, such as Cn, C12, C13 , C ₁₄ -, C ₁₅ -, C 16 -, C ₁₇ - and C ₁₈ -alcohols). As a rule, from moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, a complex mixture of addition products with different degrees of ethoxylation is formed. 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 and 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 or 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 yellow. 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, more preferably 60 days, more preferably 90 days, not more than 50% by weight, particularly preferably not more than 40% %, very particularly preferably not more than 30 wt.%, particularly preferably not more than 20 wt. % and more 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, more preferably 60 days, more preferably 90 days, not more than 50% by weight, particularly preferably not more than 40% %, very particularly 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 case, it is particularly advantageous according to the invention if the absorption maximum of a 1% solution of the colored space or the colored component is stored 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, more preferably 60 days, particularly preferably 90 days, not more than 100 wavelengths, particularly preferably not more than 50 wavelengths, completely particularly preferably not more than 30 wavelengths, particularly preferably not more than 20 wavelengths, and most 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 substance (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.

-20Possible framework formulation (Ra) and comparative formulation (Va) (data in% by weight):

Active substance ra Ra1 VA2 VA3 VA4 VA5 VA6 Ra7 phosphate (sodium tripolyphosphate) 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 (sodium perborate) 2-20 9.0 9.0 6.7 15 10 12 9 bleach activator (TAED) (Co-pentaammoniacate-CI) 0-5 2.1 2.1 3 2 1 1.5 enzyme (amylase) (Duramyl 60T) 0-5 2.0 2.0 0.7 3 3 3 2.5 enzyme (protease) (Blap 200 S) 0-5 1.8 1.8 1.0 2 2 3 2.5 phosphonate or phosphonic acid 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 aid (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 composed as follows (all other active substances as in a).

Active substance rb Rb1 VB2 VB3 vb4 VB5 VB6 Rb7 phosphate (sodium tripolyphosphate) 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

As a frame formulation (R) for the present application, the following may also be true (wt.%):

The following test formula (V) was used:

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 (sodium perborate) 2-10 7 8 5 5 bleach activator (TAED) 0-5 1 0 1 1 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

-22How the frame formulation (R) for the present application may also be valid (% by weight): The following test formulation (V) was used:

Active substance rd Rd1 Rd2 Very good 3 Very good 4 Sodium 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 (sodium perborate) 0-22 9 16 17 bleach activator (TAED) 0-25 3 1 0 20 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

As a frame formulation (R) for the present application, the following may also be true (wt.%):

The following test formula (V) was used:

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 (sodium perborate) 2-20 16 3 12 9 bleach activator (TAED) 0-5 0.5 5 2 3 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

As a frame formulation (R) for the present application, the following may also be true (wt.%):

The following test formula (V) was used:

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 (sodium perborate) 0-15 10 8 10 8 bleach activator (TAED) 0-5 1.5 2 3 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

-24How the frame formulation (R) for the present application may also apply (% 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 (sodium perborate) 2-20 10 10 6.7 10 bleach activator (Co-catalyst) 0-2 1.1 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 (sodium tripolyphosphate) 30-60 40 40 40 45 45 50 35 sodium metasilicate (5hydrate) 5-45 45 10 40 10 30 20 35

sodium metasilicate (0hydrate) 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 (trichloroisocyanuric acid) 0,5-10 1 2 2 3 1 5 5 enzyme (amylase) (Duramyl 60T) 0-5 1 2 2 2 enzyme (protease) (Blap 200 S) 0-5 1 2 2 2 nonionic surfactant (Dehypon LS 54) 0-5 2 2 2 2 3 tableting aid (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 (sodium perborate) 5-12 6 10 8 bleach activator (TAED) 0-5 1 2 0 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 the molded article according to the invention, each formulation may also mean components of one 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 the shaped articles of 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 containing the active ingredient (I) (bleach activator). 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 homogeneous (not active ingredient (I) according to the invention) and several commercially available tablets, the tablets according to the invention prevailed.

The special properties of the compositions of the invention were controlled in comparison with known compositions, for example, by storage stability.

The particular properties of the compositions according to the invention were controlled in comparison with the known compositions but also on the example of purification of the enzyme-relevant contamination.

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 on the handling of the product in conventional dishwashers has been exerted. This comparative experiment turned out particularly well. Here, the purification results were judged to be particularly advantageous.

Results with the bleach activator as active ingredient (I) were obtained in a conventional 55 ° C wash program.

Up to 20 wt. and in one case n-methylmorpholinium acetonitrile methylsulfate (MMA) and in another case TAED.

In another washing experiment, samples (according to Ra) were used which contained small amounts of metal catalysts of 0.25% by weight. (in each case a plurality of different catalysts, in particular a cobalt catalyst, specifically a cobaltpentaammonium chlorine complex) once homogeneously distributed in a tablet and once according to claim 1, so that the activator components were separated from the others (especially the enzyme-containing components and bleach-containing components). Storage stability was considerably worse after two weeks for a homogeneous tablet, so that only a poorly satisfactory cleaning effect could be determined for milk and starch contaminants. However, the tea cleaning performance of the shapes according to the invention was also better.

This five for a completely normal packaging of the bleach activator components in compartment (I), which in the present case was a recess.

Even more pronounced was the effect of using a mixture of activator and paraffin components in a standard program at 55 ° C. The cleaning results were better after production.

The effect was enhanced during storage. In particular, tea improved here, but also for milk, burnt meat, baked meat, eggs and starch mixtures, the cleaning performance was better than for molded products without range (I), homogeneously dispersed component (I) and conventional cleaners.

The effect could already be observed with paraffins with a melting point of 40-44 ° 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 57-60 ° C is particularly strong.

However, mixtures of bleach activator components and disintegrant (cellulose-based) also show better results according to the invention than homogeneous tablets.

The results clearly show that the compositions of the invention have superiority over conventional dishwasher tablets.

In other instances, melt dispersions of n-methyl morpholinium acetonitrile methyl sulfate (MMA) in readily soluble coatings have been produced which demonstrate positive effects in accelerated release.

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 Silicone oil 0.5

By heating the packaging material and mixing the active ingredient (MMA), SDE 1 to 5 melt dispersions were produced, whose composition (% by weight, based on melt) is shown in the following table:

SDE 1 SDE 2 SDE 3 SDE 4 SDE 5 Sokalan® -BM 1 * 44.0 50.0 60.0 60.0 60.0 PEG 1550 (melting point 45-50 ° C) 44.0 50.0 40.0 - - PEG 3000 (melting point 50 - 56 ° C) - - - 40.0 - PEG 4000 - - - - 40.0 citric acid 4.8 - - - - sodium bicarbonate 7.2 - - - -

* n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), approximately 50% on carrier (BASF)

The melt dispersions were filled into the shaped articles as described above and allowed to cool. Here, the shaped articles had a weight of 24 g before filling and were always filled with 1.3 g of the melt dispersion. The cleaning performance of molded articles E1 to E5 filled with melt dispersions SDE 1 to SDE 5 was tested for tea contamination. For this purpose, according to (1), tea contamination was produced and contaminated cups were cleaned in a conventional dishwasher.

1) Production of tea pollution

16 L of cold urban water (16 ° d) was briefly brought to boiling in the water preparation kettle. 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 an immersion apparatus with heating and stirrer.

the 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.

-302) Results of experiments

The cleaning performance of the tea contaminant according to Regulation (1) was visually performed and evaluated by experts, with a scale of 0 to 10 indicating no cleaning and 10 removing all stains.

'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 55 ° C / 3 ° d water hardness. Miele G 590 with a universal program was used as a dishwasher. The following table shows the achieved tea cleansing by means of E1 to E5 compared to the unfilled molded product V

IN E4 E5 E6 E7 E8 mark for 3 ° d 7.0 10,0 9.5 9.7 9.0 8.0 mark for 16 ° d 4.7 7.0 6.8 8.0 7.5 5.7

The results show that the shaped articles E1 to E5 according to the invention outweigh the comparative shaped article V in achieving tea cleansing.

Claims (24)

PATENT CLAIMS 1. A shaped article comprising activating agents, alkalinity sources, bleaching agents, enzymes and surfactants, characterized in that it contains more than 80% by weight in a space not exceeding 40% by volume. active ingredient (I) with a bleach activator component. Shaped product according to claim 1, characterized in that the space is in the range of 1 to 30% by volume, preferably in the range of 2 to 25% by volume, most preferably in the range of 3 to 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). Molded product according to claim 1, characterized in that the active ingredient (I) is a bleach activator mixture and / or a bleaching agent from the group of chlorine and / or oxygen bleaching agents and / or a silver and / or enzyme protecting agent. and / or soil release compounds and / or components to control solubility and / or other active ingredients. Molded article according to one of the preceding claims, characterized in that the at least one oxygen-based bleaching agent is selected from the group of alkali perborates, alkali percarbonates, organic peracids and hydrogen peroxide. Molded article according to one of the preceding claims, characterized in that the active ingredient (I) is composed of at least one bleach activator compound and at least one fusible component for controlling solubility selected from the group of surfactants, paraffins, microwaxes and / or high molecular weight polyethylene glycols. Shaped product according to one of the preceding claims, characterized in that the bleach activator is preferably selected from a plurality of -32 acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), Nacylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or / and / or M-NOBS) or manganese and / or cobalt complexes such as, in particular, (ammonium) cobalt complexes, (acetate) cobalt complexes, (carbonyl) cobalt complexes, cobalt or manganese chlorides, manganese sulphate preferably in amounts of from 1 wt% to 10 wt% %, in particular from 2 wt. % to 8 wt. relative to the total device. Molded article according to one of the preceding claims, characterized in that one or more activating agents selected 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 are further used. , preferably, pentasodium trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate activating agents of the class of silicates and / or metasilicates. Molded article according to one of the preceding claims, characterized in that it contains a mixture of tripolyphosphate and sodium carbonate as the activating system. Molded article according to one of the preceding claims, characterized in that it contains, as an activating additive system, a mixture of tripolyphosphate and sodium carbonate and sodium di-silicate. s Shaped product according to one of the preceding claims, characterized in that the surfactants are selected from the group of nonionic surfactants, more preferably low foaming nonionic surfactants, very particularly preferably from alkoxylated and / or propoxylated fatty alcohols, alkylpolyglycosides, alkylpolyglucamides and / or mixtures of the foregoing surfactants. Molding according to one of the preceding claims, characterized in that at least one silver protecting agent selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes is additionally present. 12. A shaped body as claimed in claim 11, wherein the silver preservative comprises benzotriazole and / or alkylaminotriazole. Molding according to claim 11, characterized in that the transition metal salts are selected from the group of salts and / or complexes of manganese and / or cobalt, particularly preferably (ammonium) cobalt complexes, (acetate) cobalt complexes, (carbonyl) - cobalt complexes, cobalt or manganese chlorides and manganese sulphate. Molding according to 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. A shaped article according to claim 14, characterized in that the dissolution time of the total shaped article is longer than the pre-wash process of a conventional dishwasher. Molding according to 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. A shaped article according to claim 16, characterized in that the dissolution time of the total shaped article is shorter than the main dishwashing time of a conventional dishwasher. Molding according to one of the preceding claims, characterized in that one of the bleaching components or the bleaching components, in particular the chlorine components, is not packaged in one phase with the perfume component. * A shaped body according to any one of the preceding claims, characterized in that the silver protection component is not packaged together with any And bleaching ingredients. Molding according to one of the preceding claims, characterized in that at least one of the components for controlling solubility is packaged together with a bleach activator. Molded article according to one of the preceding claims, characterized in that at least one of the components for controlling solubility is packaged together with enzymes. Molding according to 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 article according to 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. Molded article according to 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, more preferably with more than 70% by weight. % and in particular more than 90 wt. or a total surfactant mixture.