WO1999035229A1 - Shaped bodies of dishwashing detergent with bleach activators - Google Patents

Abstract

The invention relates to shaped bodies containing builder substances, alkali supports, bleaching agents, enzymes and tensides. The inventive high-performance shaped bodies are also very stable in storage and have a pleasant fragrance and a defined solubility profile. According to the invention, one area of the shaped body representing no more than 40 vol. % thereof contains more than 80 wt. % of the total quantity of an active substance (I) contained in the shaped body with a constituent from the group of bleach activators.

Description

 Dishwashing detergent tablets with bleach activators

The invention relates to washing or cleaning-active tablets, primarily tablets such as dishwasher tablets, detergent tablets, bleach tablets, stain remover tablets or water softening tablets for household use, in particular for mechanical use, and a process for producing these tablets and their use.

Shaped or active cleaning moldings, in particular tablets, have a number of advantages over powdered agents, such as advantageous handling, simple dosing and low packaging volume requirements.

Problems arise, however, in that relatively high compression pressures have to be used in order to achieve adequate dimensional stability and fracture resistance when compressing the powdery constituents. Due to the high compression, such tablets often have an insufficient storage stability with regard to sensitive ingredients (bleach, perfume, enzymes, silver preservatives, dyes, surfactants), a reduced performance (especially with soiling such as tea, milk, starch) compared to comparable amounts of active substance in others Form of presentation, in some cases improvable protection of sensitive materials to be cleaned and deteriorated disintegration and dissolving properties when used.

Some prior art patents are designed to avoid some of these problems.

However, the consumer is often unable to understand the performance advantages described there. Therefore, an important problem for providers of washing or cleaning-active molded articles is to satisfy consumers.

The object of the present invention was therefore powerful, easy-to-handle washing or cleaning-active molded articles, especially dishwasher tablets, detergent tablets, stain remover tablets or water softening tablets for household use, in particular for machine use with high storage stability, low packaging expenditure, good fragrance profile and defined To provide a solubility profile, which above all results in high customer satisfaction.

This was surprisingly solved by a molded article in which an ingredient (I) with a component from the group of bleach activators is predominantly provided in a defined area, this area not representing more than 40% by volume of the molded article.

The application is therefore a molded article containing builders, alkali carriers, bleaching agents, enzymes and surfactants, characterized in that in an area not greater than 40 vol .-%, more than 80 wt .-%, an active substance (I) with one ingredient from the group of bleach activators is included.

In addition to the agent from the group of bleach activators, the ingredient (I) can additionally be an oxygen or chlorine-based bleach, a silver preservative and / or a soil release compound, an enzyme, a surfactant or a component or a compound for solubility control. The ingredient (I) can also be a mixture of several of these ingredients.

It is particularly preferred if the ingredient (I) is a mixture of a component or a compound for solubility control, in addition to the agent from the group of bleach activators and at least one other ingredient from the group consisting of bleach and / or silver protection agent and / or Soil-release compound and / or enzyme and / or a surfactant.

The solubility of the area with the ingredient (I), the surface and the type of corrosion and the storage stability can also have a decisive influence on the properties of the tablet.

For the purposes of the present invention, it is favorable if the range contains more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, very particularly preferably the total amount of an ingredient (I) present is surrounded by other ingredients of the molded body in exactly three spatial directions.

It is also preferred within the scope of the present invention if at least one region with more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, very particularly preferably the total amount of one present Ingredient (I) is present, which dissolves more than 5%, preferably more than 10%, very particularly preferably more than 25%, very particularly preferably more than 50% and very preferably more than 100% faster than the and / or the remaining areas of the molded body.

It is also positive if in an area with no more than 40% of the surface, preferably between 5 and 30%, particularly preferably between 10 and 25%, very particularly preferably between 15 and 20% by volume of the molded body, more than 80% by weight. %, preferably more than 90% by weight, particularly preferably more than 95% by weight, very particularly preferably the total amount of an ingredient (I) present.

A desirable effect on the overall result can also be obtained by increasing the weight of the area with no more than 40% of the surface containing more than 80% by weight of an ingredient (I) when stored under normal household conditions, i.e. H. between 15 and 30 ° C. and between 5 and 55% atmospheric humidity, preferably 15 and 35% atmospheric humidity for a period of 30 days, preferably 60 days, particularly preferably 90 days, not more than 50% by weight, preferably not more than 40% %, very particularly preferably not more than 30% by weight, extremely preferably not more than 20% by weight and extremely preferably not more than 10% by weight, at best not more than 5% by weight.

A desirable effect on the overall result can also be obtained if the loss of active substance (I) in the area when stored under normal household conditions, i. H. between 15 and 30 ° C. and between 5 and 55% atmospheric humidity, preferably 15 and 35% atmospheric humidity for a period of 30 days, preferably 60 days, particularly preferably 90 days, not more than 50% by weight, preferably not more than 40% %, very particularly preferably not more than 30% by weight, extremely preferably not more than 20% by weight and extremely preferably not more than 10% by weight, at best not more than 5% by weight.

A desirable influence on the overall result can also be achieved if the absorption maximum of a 1% solution of a colored area or a colored component when stored under normal household conditions, ie between 15 and 30 ° C. and between 5 and 55% atmospheric humidity, preferably 15 and 35% humidity for a period of 30 days, preferably 60 days, especially preferably 90 days not more than 100 wave numbers, preferably not more than 50 wave numbers, very particularly preferably not more than 30 wave numbers, extremely preferably not more than 20 wave numbers and most preferably not more than 10 wave numbers, at best not more than 5 wave numbers.

The molded body according to the invention also has a positive effect if the region with more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, very particularly preferably the total amount of an ingredient present ( I) is surrounded by other ingredients of the molded body in exactly three spatial directions.

Solubility:

The solubility can be influenced by components and / or compounds to accelerate solubility (disintegrant) or to delay solubility.

All disintegrants known in the prior art can be used as disintegrants. Particular reference is made to the textbooks Rompp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987). Substances such as starch, cellulose and cellulose derivatives, alginates, Dextran, cross-linked polyvinylpyrrolidones and others; systems of weak acids and carbonate-containing agents, in particular citric acid and tartaric acid in combination with bicarbonate or carbonate as well as polyethylene glycol sorbitan fatty acid esters.

International patent application WO-A-96/06156 also states that the incorporation of disintegrants in detergent or cleaning agent tablets can be advantageous. Again, microcrystalline cellulose, sugars such as sorbitol, but also sheet silicates, in particular finely divided and swellable sheet silicates of the bentonite and smectite type, are mentioned as typical disintegrants. Substances contributing to gas formation such as citric acid, bisulfate, bicarbonate, carbonate and percarbonate are also listed as possible disintegration aids.

The European patent applications EP-A-0 466 485, EP-A-0 522 766, EP-A-0 711 827, EP-A-0 711 828 and EP-A-0 716 144 describe the production of cleaning-active Tablets described, using compact, particulate material with a particle size between 180 and 2000 microns. The resulting tablets can have both a homogeneous and a heterogeneous structure. According to EP-A-0 522 766, at least the particles which contain surfactants and builders are coated with a solution or dispersion of a binder / disintegrant, in particular polyethylene glycol. Other binders / disintegrants are, in turn, the disintegrants already described and known several times, for example starches and starch derivatives, commercially available cellulose derivatives such as crosslinked and modified cellulose, microcrystalline cellulose fibers, crosslinked polyvinylpyrrolidones, layered silicates etc. Also weak acids such as citric acid or tartaric acid, which in In connection with carbonate-containing sources when they come into contact with water lead to bubbling effects and according to the definition according to Römpp belong to the second class of disintegrants can be used as coating material.

Particular reference is made to the unpublished DE 197 10 254, which describes disintegrants whose particle size distribution (sieve analysis) is designed in such a way that a maximum of 1% by weight, preferably less, of dust components is present and overall (including any dust components present) less than 10% by weight of the disintegrant granules are smaller than 0.2 mm. At least 90% by weight of the disintegrant granules advantageously have a particle size of at least 0.2 mm and a maximum of 3 mm. These disintegrants are particularly suitable for the present invention. Detergent tablets containing disintegrants in granular or, if appropriate, cogranulated form are also described in German patent applications DE 197 09 991 (Stefan Herzog) and international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above-mentioned and coarser cellulose-based disintegration aids described in the cited documents are within the scope of the present invention preferably used as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier.

Agents from the group of organic acids, such as. B. citric acid, or a mixture of citric acid / bicarbonate and / or the celluloses and cellulose derivatives. If an explosive is contained in the molded article, the dissolution time of the entire molded article is preferably shorter than the duration of the main wash cycle of a conventional dishwasher, that is to say shorter than 40 minutes, particularly preferably shorter than 30 minutes, very particularly preferably shorter than 20 minutes and extremely preferably shorter than 10 min.

It is particularly preferred in the context of the present invention if the region which is more rapidly soluble according to the invention contains at least one acidifying agent. Examples of acidifying agents are boric acid and

Alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid and succinic acid are preferred from this group. Malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

In the context of the present invention, preference is given to detergent tablets in which a substance from the group of the organic di-, tri- and oligocarboxylic acids or mixtures thereof are used as the acidifying agent in the more rapidly dissolving region, the use of citric acid being particularly preferred . The acidifying agents mentioned are preferably either sole component I or at least part of the same. It is therefore preferred within the scope of the present invention if at least 80 % By weight, preferably more than 90% by weight, particularly preferably more than 95% by weight and very particularly preferably the total amount of the acidifying agent contained in the molded body are in the more rapidly soluble region.

In addition to the acidifying agent, the more rapidly dissolving region in preferred embodiments of the present invention can contain further ingredients, for which the criterion applicable to ingredient I is also advantageously to be used, that is to say that at least 80% by weight, preferably more than 90, of these ingredients also applies % By weight, particularly preferably more than 95% by weight and very particularly preferably the total amount of the total ingredient contained in the molded body are in the more rapidly soluble region. As already mentioned above, further ingredients are, for example, carbonates and / or hydrogen carbonates, the use of which, in combination with acidifying agents, leads to a gas release upon contact with water, which further reduces the dissolution times. Such an effervescent system can be formulated with an excess of acidifying agent, which enables an acidic pre-rinse cycle, but other ingredients can also be incoφorated in the more quickly soluble area, so that the effervescent system releases the other ingredients more quickly. If shower systems are used, the dissolving time of the more rapidly dissolving area is preferably still below the values mentioned above, i.e. less than 10 min, preferably less than 5 min and in particular less than 2 min. Such quick-dissolving areas can bring significant benefits to cleaning performance.

Paraffins and / or microwaxes and or the high molecular weight polyethylene glycols, which are described in detail in the prior art, are generally used as the material for delaying dissolution. The use of mixtures as mentioned in the unpublished publication DE 197 27 073 and the disclosure of which is hereby expressly incorporated into this document is particularly suitable for the present application.

If a component for delaying dissolution is included, the dissolution time of the entire molded body in 20 ° C. cold water is longer in a preferred embodiment than the pre-rinse cycle of a commercially available dishwasher, i.e. longer than 5 min, preferably longer than 10 min. In such cases, a smaller area of the molded body can be delayed in release, so that the majority of the molded body makes up the more rapidly soluble area. Such measures to delay dissolution can only release certain ingredients, for example, only in the rinse cycle, whereby further advantages in cleaning performance can be achieved.

Instead of a component for delayed release, a component for accelerating release can also be used. Such components preferably originate from the group of polyethylene glycols with molecular weights between 1500 and 4000, preferably between 1500 and 3000.

General forms of presentation:

All possible three-dimensional bodies are suitable for the spatial shape of the shaped body, such as are listed in the prior art patents and the standard works of the specialist literature (for example: Riedel, "Die Tablette") but also in the prior art patents. The area in which the ingredient (I) is contained is also not tied to a specific spatial form. For practical reasons, however, an expansion in a spatial direction of more than 5 mm is preferred.

Specific forms of presentation:

In a preferred embodiment of the invention, homogeneous or heterogeneous molded bodies of known design are provided.

These include in particular cylindrical tablets, these tablets preferably having 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. Shaped bodies with a diameter of 32, 33, 34, 35, 36, 37, 38 and 39 mm have proven to be particularly favorable. In special designs, the height is 24, 25, 26, 27 or 28 mm.

Square, rectangular, trapezoidal, oval and irregularly shaped base areas can also be used with preference. The edge lengths are preferably between 15 to 60 mm, in particular 30 +/- 10 mm. The weight of the individual shaped bodies, in particular the tablets, is preferably 15 to 60 g and in particular 20 to 40 g per shaped body or tablet; the consistency of the molded body or tablets, however, usually has values above 1 kg / dm, preferably from 1.1 to 1.4 kg / dm.

Depending on the type of application, the water hardness range or the level of contamination, 1 or more, for example 2 to 4, shaped bodies, in particular tablets, can be used. Further shaped bodies according to the invention can also have smaller diameters or dimensions, for example around 10 mm.

A homogeneous molded body is understood to mean those in which the ingredients of the molded body are homogeneously distributed except for the area with ingredient (I) in such a way that no different ingredients and / or active ingredients are perceptible to the naked eye. The grain structure of the solids used can of course still be recognized. In a preferred embodiment of the invention, in addition to the area with the ingredient (I), only a further area (phase) is present,

Heterogeneous shaped bodies are accordingly understood to mean those which do not have a homogeneous distribution of the ingredients present in addition to the ingredient (I). In a simple case, heterogeneous shaped bodies can be produced, for example, by the different ingredients having different colors and / or carrying a different fragrance component.

Another case, which according to the invention is to be counted as the non-uniform (heterogeneous) molded bodies, comprises an embodiment in which a molded body is pressed which, in addition to the area with the ingredient (I), has several layers (phases), that is to say at least two layers. It is e.g. B. possible that these different layers have different disintegration and dissolution rates and / or carry different ingredients. This can result in advantageous application properties of the molded body. If, for example, ingredients are contained in the moldings that mutually influence each other, it is possible to separate them. If a defined sequence of cleaning conditions is to be created in a machine, it is possible to use one (or integrate several component (s) in one (or the) more rapidly disintegrating and / or more quickly soluble layer and incorporate the other component (s) in one (or) the more slowly disintegrating layer (s) so that one component can work with lead time or has already reacted if another goes into solution.

A preferred embodiment of the invention consists in that in addition to the area with the ingredient (I) there are two further phases. It is particularly advantageous if the volume ratios of the two further phases are between 10: 1 and 1:10, 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 further phases are present.

The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely detached or disintegrated; however, complete and or partial encapsulation of the inner layer (s) can also be achieved by the layers lying further outside, which leads to a prevention and / or delay in the early dissolution of components of the inner layer (s).

In a further preferred embodiment of the invention, a tablet consists of at least three layers, that is to say two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while in the case of the tablet in the form of a tablet, the two outer layers and in the case of the envelope However, the outermost layers of the tablet are free of peroxy bleach. It is also possible to spatially separate peroxy bleaching agents and any bleach activators or bleach catalysts and / or enzymes present in a tablet / molded article. Such configurations have the advantage that no undesired interactions would be feared in the molded bodies according to the invention.

Another cheap and preferred embodiment of the invention is that one of the bleaching component or components, especially the chlorine component, is not assembled together with the perfume component in one phase. Another cheap and preferred embodiment of the invention is that the Silver protection component is not made up with one or more of the bleaching components. Another cheap and preferred embodiment of the invention is that one of the component or components for solubility control is assembled together with the bleach activator. Another cheap and preferred embodiment of the invention is that one of the component or components for solubility control is made up together with the enzymes. Another cheap and preferred embodiment of the invention is that one of the component or components for solubility control is made up together with the bleach. Another cheap and preferred embodiment of the invention is that one of the component or components for solubility control is assembled together with the silver protection component. Another cheap and preferred embodiment of the invention consists in that one of the component or components for solubility control together with at least 50 wt .-%, preferably more than 70 wt .-%, particularly more than 90 wt .-% of a surfactant or the total surfactant mixture is assembled.

The preparation of the agents according to the invention is carried out according to the usual methods of molding production.

In some embodiments, it has proven to be particularly advantageous to fill the area with the ingredient (s) in the form of a liquid (generally through solution and / or melt), if appropriate at elevated temperatures, into a prefabricated recess in the surrounding ingredients and then through conventional ones technical measures to freeze this area (generally by drying and / or cooling). A viscosity of more than 1500 mPas, preferably more than 2000 mPas, particularly preferably between 2000 and 15000 mPas, very particularly preferably between 2500 and 7000 mPas and extremely preferably between 3000 and 4000 mPas has proven particularly useful.

The combination of the active ingredient (I) with meltable carrier substances has proven particularly effective. In principle, this includes all substances with a solidification point at or especially above room temperature.

Non-ionic surfactants (Dehypon® LT 104, Dehypon® LS 54, Dehydol® LS 30, Lutensol® AT 80) are particularly suitable for the purposes of the present invention. Polyethylene glycols with different molecular weights (PEG 400, 12000), soaps (Lorol® C 16), stearates (Cutina® GMS), but also thickened sodium hydroxide solution and meltable salts, such as sodium carbonate - decahydrate. The advantages and disadvantages of the individual ingredients can be understood by the expert on the basis of tests.

The use of mixtures as mentioned in the unpublished publication DE 197 27 073 and the disclosure of which is hereby expressly incorporated into this document is particularly suitable for the present application.

In other embodiments, parts of the molded body and / or components of the molded body are treated by irradiation with microwaves in order to positively influence strength, moisture content and solubility.

But a simple pressing of the components is also possible. In addition to powders and granules, microtabs and molded articles of smaller dimensions than the final molded article can also be used.

Specific ingredients:

Special ingredients (I) which are used in the context of the invention are bleach activators. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances 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, l, 5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine DADHT and isatoic anhydride ISA.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-Moφholinium-acetonitrile-methylsulfate (M and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally 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 are known. The hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.

In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleaching catalysts. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 , Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium known from German patent application DE 196 20 411 Amine complexes, the manganese, copper and cobalt complexes described in German patent application DE 44 16 438, the cobalt complexes described in European patent application EP 0 272 030, the manganese complexes known from European patent application EP 0 693 550, the manganese, iron, cobalt and copper complexes known from European patent EP 0 392 592 and / or those described in European patent EP 0 443 651 or European patent applications EP 0458397, EP 0 458398, EP 0 549271, EP 0 549 272, EP 0 544 490 and EP 0 544 519 described manganese complexes. 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. Bleach activators from the group of multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n-) or iso-NOBMA are preferred , preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, based on the total composition, used.

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

Special ingredients (I) that are used in the context of the invention are substances that connect the re-soiling of surfaces and / or facilitate the removal of dirt after a single application (so-called “soil release compounds”). The soil release compounds used according to the invention include all compounds known in the prior art. Cationic polymers such as those used for. B. are known from the following publications:

In EP-A-0 167 382, EP-A-0 342 997 and DE-OS-26 16 404 cleaning agents are added cationic polymers in order to achieve a streak-free cleaning of the surfaces.

EP-A-0 167 382 describes liquid detergent compositions which can contain cationic polymers as thickeners. Hydroxypropyltrimethylammonium guar; Copolymers of aminoethyl methacrylate and acrylamide and copolymers of dimethyldiallylammonium chloride and acrylamide are described.

EP-A-0 342 997 describes general-purpose cleaners which can contain cationic polymers, in particular polymers with imino groups being used.

DE-OS-26 16 404 describes cleaning agents for glass which contain cationic cellulose derivatives. The addition of the cationic cellulose derivatives in the agents a better drainage of the water in order to obtain streak-free cleaned glass.

In EP-A-0 467 472 e.g. B. cleaning agents for hard surfaces are described which contain cationic homo- and / or copolymers as soil-release polymers. These polymers have quaternized ammonium alkyl methacrylate groups as monomer units. These connections are used to equip the surfaces in such a way that the dirt can be removed more easily during the next cleaning process.

The cationic polymers are particularly preferably selected from cationic polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiamrononium salts; polymer-analogous reaction products of ethers or esters of polysaccharides with ammonium side groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethylene imine polymers and polyesters and polyamides with quaternary side groups as soil release compounds. In the context of this application, natural polyuronic acids and related substances, as well as polyampholytes and hydrophobized polyampholytes, or mixtures of these substances, are also exceptionally preferred.

According to the invention, between 0 and 5% by weight of enzymes, based on the entire preparation, can be added to the cleaning agent in order to increase the performance of the cleaning agents or to guarantee the same quality of cleaning performance under milder conditions. The most commonly used enzymes include lipases, amylases, cellulases and proteases. Preferred proteases are e.g. B. BLAP® 140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo. Particularly suitable cellulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk. Duramyl® and Termamyl® 60 T and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades find particular use as amylases. Other enzymes can also be used.

Particular ingredients (I) which are used in the context of the invention are oxygen bleaching agents, preferably the alkali metal perborates and their hydrates and the alkali metal percarbonates, sodium perborate, as mono- or tetrahydrate, or sodium percarbonate and their hydrates preferably being used in the context of the invention. The persulphates can also be used.

Typical oxygen bleaches are also organic peracids. The organic peracids used with preference include above all the excellently active phthalimidoperoxycaproic acid, but in principle all other known peracids can also be used.

Dishwashing detergents according to the invention can contain corrosion inhibitors as ingredient (I) to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the field of automatic dishwashing. The known subsets of the prior art, such as. B. described in DE 43 25 922, DE 41 28 672 or DE 43 38 724. In general, silver protection agents can be selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corrosion of the silver surface. In chlorine-free cleaners, especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

Other ingredients:

In the shaped bodies according to the invention, all of the ingredients (I) described above can also take on the function of other ingredients if the condition of the inventive area is met by other ingredients.

In the cleaning agents according to the invention, water-soluble and water-insoluble builders can be used especially for binding calcium and magnesium. Water-soluble builders are preferred because they generally have less tendency to form insoluble residues on dishes and hard surfaces. Customary builders, which can be present in the scope of the invention between 10 and 90% by weight, based on the entire preparation, are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates. Water-insoluble builders include the zeolites, which can also be used, as well as mixtures of the abovementioned builders. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates are preferably used.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates are considered to be alkali carriers.

Alkali metal sesquicarbonates, alkali silicates, alkali metasilicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention.

A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.

A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.

In principle, all surfactants can be used as surfactants. Preference is given to the nonionic surfactants and in particular the low-foaming nonionic surfactants, but other low-foaming surfactants are also suitable. The alkoxylated alcohols, particularly the ethoxylated and or propoxylated ones, the alkyl polyglycosides and the alkyl polyglucamides are particularly preferred.

The person skilled in the art generally understands by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols (Cio to Cι ₈ , preferably between Cj ₂ and Cι ₆ , such as Cn-, C ₁₂ -, C ₁₃ -, Cj ₄ -, Cι -, Cι ₆ -, Cιτ- and Cι - alcohols). As a rule, n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used in the context of the invention. Very particularly preferred in For the purposes of the present invention, highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates are.

Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols using the relevant methods of preparative organic chemistry, with a mixture of monoalkylated, oligomeric or polymeric sugars depending on the type of preparation. Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols and the degree of oligomerization of the sugars being between 1 and 10.

Fatty acid polyhydroxylamides (glucamides) are acylated reaction products of the reductive amination of a sugar (glucose) with ammonia, whereby long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid chlorides are generally used as acylating agents. Secondary amides are formed when reducing with methylamine or ethylamine instead of with ammonia, such as. B. in SÖFW-Journal, 119, (1993), 794-808. Carbon chain lengths from C ₆ to C ₂ in the fatty acid residue are preferably used.

The areas of the molded body can be colored. It is particularly preferred if one or more or all areas of the molded body are colored differently in the molded body. In one special embodiment of the molded body, the color is red. In another special embodiment of the molded body, the color is green. In another special embodiment of the molded body, the color is yellow. In another special embodiment of the molded body, the color is a mixture of different colors.

The storage stability of the molded body is particularly important. It is particularly preferred according to the invention if the increase in the weight of the ingredient (I) during storage under normal household conditions, ie between 15 and 30 ° C. and between 5 and 55% atmospheric humidity, preferably 15 and 35% atmospheric humidity for a period of 30 days. preferably 60 days, particularly preferably 90 days not more than 50% by weight, preferably not more than 40% by weight, very particularly preferably not more than 30% by weight, extremely preferably not more than 20% by weight and most preferably not more than 10% by weight, at best not more than 5% by weight. It is also particularly preferred according to the invention if the loss of active substance of the ingredient (I) during storage under normal household conditions, ie between 15 and 30 ° C. and between 5 and 55% atmospheric humidity, preferably 15 and 35% atmospheric humidity, for a period of 30 days , preferably 60 days, particularly preferably 90 days not more than 50% by weight, preferably not more than 40% by weight, very particularly preferably not more than 30% by weight, extremely preferably not more than 20% by weight and most preferably not more than 10% by weight, at best not more than 5% by weight.

It is also particularly preferred according to the invention if the absorption maximum of a 1% solution of a colored area or a colored component during storage under normal household conditions, ie between 15 and 30 ° C. and between 5 and 55% humidity, preferably 15 and 35% humidity for the duration of 30 days, preferably 60 days, particularly preferably 90 days not more than 100 wave numbers, preferably not more than 50 wave numbers, very particularly preferably not more than 30 wave numbers, extremely preferably not more than 20 wave numbers and extremely preferably not more than 10 At best, wave numbers are not more than 5 wave numbers.

Examples

The following recipes were mixed and pressed into shaped bodies. In the

Ingredients given in brackets are examples of the substance class but can be replaced by other substances listed in the application. The

Frame formulations represent preferred areas of the invention.

When measuring the effectiveness, the selected ingredient (I) was transferred to the area according to the invention. In the other area (the other areas) it was reduced according to the invention, or left out entirely before the investigations were carried out.

A possible framework recipe (Ra) and test recipes (Va) (in% by weight):

Das Buildersystem der obigen Rahmenrezeptur kann auch folgendermaßen zusammengesetzt werden (alle anderen Inhaltsstoffe gleich, wie bei a).

The builder system of the framework recipe above can also be composed as follows (all other ingredients are the same as in a).

The following can also be used as the basic formulation (R) for the present application (% by weight): The following was used as the test formulation (V):

Als Rahmenrezeptur (R) für die vorliegende Anmeldung kann auch gelten (Gew.-%): Als Versuchsrezeptur (V) wurde genutzt:

The following can also be used as the basic formulation (R) for the present application (% by weight): The following was used as the test formulation (V):

The following can also be used as the basic formulation (R) for the present application (% by weight): The following was used as the test formulation (V):

The following can also be used as the basic formulation (R) for the present application (% by weight): The following was used as the test formulation (V):

The following can be used as the basic formulation (R) for this application (details in wt.

%):

The following test formulation (V) was used:

The following can be used as the basic formulation (R) for the present application (details in weight

%):

The following test formulation (V) was used:

A further basic formulation (R) (% by weight) and experimental formulations (V) were tested:

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

Of course, each of the recipes can also contain other ingredients that are common in MGSM (e.g. fillers, preservatives, etc.) in extremely small quantities, with the other ingredients being proportionately varied accordingly.

The production of the molded body according to the invention uses steps which are known in a different context to the knowledge of the person skilled in the art in this field. A preferred embodiment of the molded body of the first claim contains a depression in a tablet, this depression containing the ingredient (I) (bleach activator). In a preferred case, the production takes place in such a way that an indentation is embossed into a molded body and this indentation is filled. The embossing can be done on a Rotary presses from Korsch. In the present case, a tablet press from Fette was used. A round tablet shape (26 X 36 mm) was selected and embossed on one side with a stamp 5 mm deep, the base area being chosen such that a volume of 1 ml could be filled in and the tablet subsequently had a smooth surface.

A liquid mixture of paraffin and an active ingredient (I) was then introduced and allowed to cool. This cooling can be supported by common equipment methods.

As already mentioned, the ingredient (I) according to the invention was previously reduced in quantity in the corresponding recipe which surrounds the filled area and was omitted in the surrounding areas in the examples and investigations at hand.

In comparison tests with homogeneous (noninventive ingredient (I)) and some commercially available tablets, the tablets according to the invention proved to be superior.

The special properties of the agents according to the invention were compared with known agents using the example of storage stability.

The special properties of the agents according to the invention were also compared to known agents but also examined using the example of cleaning enzyme-relevant soiling.

In addition, the special properties of the agents according to the invention were checked by technically untrained persons under practical conditions in comparison to homogeneous tablets. Apart from instructions for the dosage and general safety instructions, no influence was taken on the handling of the agents by the group of people in standard dishwashers. This comparison test turned out to be particularly good. The cleaning results were rated as particularly favorable here.

The results with a bleach activator as active ingredient (I) were achieved in a conventional 55 ° C rinse program. In a mixture according to the formula Ra or Val, independently of one another up to 20% by weight and in one case n-methyl-Moφholinium-acetonitrile-methyl sulfate (MMA) in another case TAED was used as the bleach activator component.

In a further washing test, samples (according to Ra) containing small amounts of metal catalysts 0.25% by weight & (several different Mn catalysts in each case, but especially cobalt catalyst, specifically the cobalt pentammine chloro complex) were found once in the tablet in a homogeneous distribution and once used according to claim 1, so that the activator component was largely separated from other (especially. enzyme-containing components and bleach-containing components). The storage stability after two weeks was significantly worse in the case of the homogeneous tablet, so that only a little satisfactory cleaning effect on milk and more soiling was found. But the cleaning performance of tea was also better in the embodiment according to the invention

This applies to the normal assembly of the bleach activator component in area (I), which in the present case represented a hollow.

The effect becomes even clearer when using a mixture of activator component and paraffin in a standard program at 55 ° C. The cleaning results were better immediately after production. The effect increased with storage. Tea in particular shows improvements here, but milk, burnt-in meat, burned-in meat, egg and starch mixtures also showed better cleaning performance than molded articles without area (I), homogeneously distributed component (I) and commercially available cleaners.

The effect was already seen with paraffins with a melting point of 40-44 ° C. The effect is more pronounced with paraffins with a melting point of 46-48 ° C. The cleaning effect of paraffins with a melting point of 57-60 ° C is also clearly visible.

However, mixtures with bleach activator component and disintegrant (cellulose base) also showed better results according to the invention than homogeneous tablets.

The results clearly show that the agents according to the invention are superior to conventional dishwasher tablets. In further examples, melt dispersions of n-methyl-Moφholinium-acetonitrile-methyl sulfate (MMA) were produced in easily soluble coating substances, which demonstrate the positive effects with accelerated release.

Here, trough-shaped bodies (weight: 24 g) were produced by pressing with a press ram which had a pin. Table 1 below shows the composition (in% by weight, based on the premix) and thus the mold body:

Table 1: Composition of the premix (% by weight):

By heating the respective coating material and stirring in the active substance (MMA), melt dispersions SDE 1 to 5 were prepared, the composition (% by weight, based on the melt) of which is given in the table below:

* n-methyl-Moφholinium-acetonitrile-methyl sulfate (MMA), approx. 50% on carrier (BASF)

The melt dispersions were introduced into the moldings in the manner mentioned above and allowed to cool. Here, the molded articles had a weight of 24 g before filling and were each filled with 1.3 g of the melt dispersion. The cleaning performance of the molded bodies El to E5 filled with the melt dispersions SDE 1 to SDE 5 was tested on tea soiling. For this purpose, a tea stain was produced according to (1) and the soiled cups were cleaned in a household dishwasher:

(1) Production of tea soiling

16 l of cold city water (16 ° d) are briefly heated to boiling in a water treatment boiler. 96 g of black tea are drawn in the nylon net with the lid closed for 5 minutes and the tea is transferred to a diving apparatus with heating and agitator.

60 teacups are dipped into the prepared tea brew 25 times at one-minute intervals at 70 ° C. The cups are then removed and placed on a tray with the opening facing down to dry.

(2) Test results

The cleaning performance of the agents for the soiling of tea according to the instructions under (1) was carried out visually by experts and graded, with a scale of 0-10 the mark "0" means no cleaning and "10" means complete removal of the stains.

The teen notes were both for washing conditions 55 ° C / 16 ° d water hardness

Main wash cycle measured (i.e. "harsh conditions") as well as for 55 ° C / 3 ° d

Water hardness. A Miele G 590 with a universal program was used as the dishwasher.

The table below shows the tea cleaning achieved by means E1 to E5 in comparison to an unfilled molded article V

The results show that the molded bodies E1 to E5 according to the invention are far superior to the comparative molded bodies V when cleaning tea.

Claims

Claims: 1. Shaped body containing builders, alkali carriers, bleaching agents, enzymes and surfactants, characterized in that in a range not greater than 40 vol .-%, more than 80 wt .-%, an active substance (I) with a component from the group of Bleach activators is included. 2. molded body according to claim 1, characterized in that the range between 1 and 30 vol .-%, particularly preferably between 2 and 25 vol .-%, very particularly preferably between 3 and 20 vol .-% of the molded body more than 90 wt %, particularly preferably more than 95% by weight, very particularly preferably the total amount of an ingredient (I) present. 3. molded article according to claim 1, characterized in that this ingredient (I) is a mixture of bleach activator and or bleach from the group of chlorine and / or oxygen bleach and / or silver protection agent and / or enzyme and / or soil-release compound and / or a component for solubility control and / or other ingredients. 4. molded article according to any one of the preceding claims, characterized in that at least one oxygen bleaching agent selected from the group of alkali perborates, alkali percarbonates, organic peracids and hydrogen peroxide is contained. 5. Molded body according to one of the preceding claims, characterized in that the ingredient (I) contains at least one bleach activator compound and at least one fusible component for solubility control selected from the group of surfactants, paraffins, microwaxes and / or the higher molecular weight polyethylene glycols. 6. molded article according to any one of the preceding claims, characterized in that a bleach activator, preferably from the group of polyacylated alkylenediamines, especially tetraacetylethylene diamine (TAED),,-acylimides, especially Ν-Νonanoylsuccinimide (ΝOSI), acylated phenolsulfonates, especially n Anonanoyl or isononanoyloxybenzenesulfonate (n- or iso-ΝOBS), MMA and or the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese, of manganese sulfate, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent 7. molded article according to any one of the preceding claims, characterized in that one or more builders 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, preferably trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and or metasilicates is used. 8. Molded body according to one of the preceding claims, characterized in that contains a mixture of tripolyphosphate and sodium carbonate as the builder system. 9. molded article according to one of the preceding claims, characterized in that a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is included as the builder system. 10. Molded body according to one of the preceding claims, characterized in that the surfactants are selected from the group of nonionic surfactants, preferably the low-foaming nonionic surfactants, very particularly preferably the alkoxylated and / or propoxylated fatty alcohols, the alkyl polyglycosides, the alkyl polyglucamides and / or mixtures of the above surfactants. 1 1. Shaped body according to one of the preceding claims, characterized in that it additionally contains at least one silver protective agent selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes. 12. Molded body according to claim 11, characterized in that benzotriazole and / or alkylaminotriazole is contained as silver protective agent. 13. molded article according to claim 11, characterized in that the transition metal salts are selected from the group of manganese and / or Cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and the manganese sulfate. 14. Molded body according to one of the preceding claims, characterized in that the component and / or the components for solubility control selected from the group of paraffins, the micro waxes and the high molecular weight polyethylene glycols are included. 15. molded article according to claim 14, characterized in that the dissolution time of the entire molded article is longer than the duration of the pre-wash cycle of a conventional dishwasher. 16. Molded body according to one of claims 1 to 13, characterized in that the component and / or the components for solubility control selected from the group of organic acids, such as. B. citric acid, or a mixture of citric acid / bicarbonate and / or the celluloses and cellulose derivatives are contained. 17. molded article according to claim 16, characterized in that the dissolution time of the entire molded article is shorter than the duration of the main wash cycle of a conventional dishwasher. 18. Molded body according to one of the preceding claims, characterized in that one of the bleaching component or components, especially the chlorine component, is not assembled together with the perfume component in one phase. 19. Molded body according to one of the preceding claims, characterized in that the silver protection component is not made up with one of the bleaching components. 20. Molded body according to one of the preceding claims, characterized in that one of the component or components for solubility control is assembled together with the bleach activator. 21. Molded body according to one of the preceding claims, characterized in that one of the component or components for solubility control is assembled together with the enzymes. 22. Molded body according to one of the preceding claims, characterized in that one of the component or components for solubility control is assembled together with the bleaching agent. 23. Molded body according to one of the preceding claims, characterized in that one of the component or components for solubility control is assembled together with the silver protection component. 24. Molded body according to one of the preceding claims, characterized in that one of the component or components for solubility control together with at least 50 wt .-%, preferably more than 70 wt .-%, particularly more than 90 wt .-% of a surfactant or Total surfactant mixture is made up.