DE19758180A1 - Detergent tablets 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

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, especially for mechanical use, and a method for producing these moldings and their Use.

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

However, problems arise from the fact that in order to achieve a sufficient shape and Resistance to breakage when pressing the powdery components is relatively high Press prints must be applied. Show due to the strong compaction such tablets often have insufficient storage stability with regard to sensitive Ingredients (bleach, perfume, enzymes, silver preservatives, dyes, surfactants), one reduced performance (especially with soiling such as tea, milk, starch) in comparison to comparable amounts of active substance in another 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 address some of these problems be solved avoidably.

Often, however, the consumer cannot achieve the performance advantages described there comprehend. Therefore, there is an important problem for providers of washing or cleaning active moldings to satisfy consumers.

The object of the present invention was therefore powerful, easy to handle washing or cleaning active moldings, especially dishwasher tablets, Detergent tablets, stain remover tablets or water softening tablets for the Household use, especially for machine use with high Storage stability, low packaging costs, 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 body in which an ingredient (I) was mainly provided in a defined area, but this area was not represents more than 40% by volume of the shaped body.

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

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

It is particularly preferred if the ingredient (I) is a mixture of one 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 is a surfactant.

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

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, entirely particularly preferably the total amount of an existing ingredient (I) in exactly three Spatial directions are surrounded by other ingredients of the molded body.

It is also preferred in the context of the present invention if at least one Range with more than 80 wt .-%, preferably more than 90 wt .-%, particularly preferably more than 95% by weight, very particularly preferably the total amount of one present Ingredient (I) is present, which is more than 5%, preferably more than 10%, entirely particularly preferably more than 25%, very particularly preferably more than 50% and extremely preferably more than 100% faster than 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%, entirely particularly preferably between 15 and 20% by volume of the shaped 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 existing ingredient (I) is contained.

A desirable influence on the overall result can also be achieved Weight gain of the area with no more than 40% of the surface containing more than 80 wt .-% of an ingredient (I) when stored under normal household conditions, d. H. between 15 and 30 ° C and between 5 and 55% humidity, preferably 15 and 35% Air humidity for a period of 30 days, preferably 60 days, particularly preferably 90 Days not more than 50 wt .-%, preferably not more than 40 wt .-%, 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 is.

A desirable influence on the overall result can also be achieved if the Loss of active substance (I) of the area when stored under normal household conditions, d. H. between 15 and 30 ° C and between 5 and 55% humidity, preferably 15 and 35% 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 preferred not more than 20% by weight and most preferably not more than 10% by weight at best is not more than 5% by weight.

A desirable influence on the overall result can also be achieved if that Absorption maximum of a 1% solution of a colored area or a colored one Component when stored under normal household conditions, d. H. 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 wavenumbers, preferably not more than 50 wavenumbers, very particularly preferred not more than 30 wavenumbers, most preferably not more than 20 wavenumbers and most preferably not more than 10 wavenumbers, at best not more than 5 Wavenumbers is.

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

solubility

The solubility can be increased by components and / or compounds Accelerated solubility (disintegrant) or delayed solubility become.  

All disintegrants known in the prior art can be used as disintegrants Find. Particular reference is made to the textbooks Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987). Particularly suitable are substances such as starch, cellulose and cellulose derivatives, alginates, dextrans, cross-linked polyvinylpyrrolidones and others; Systems from weak acids and carbo natural agents, especially citric acid and tartaric acid in combination with hydro gene carbonate or carbonate as well as polyethylene glycol sorbitan fatty acid ester.

The use of explosives is also found in the patent literature. So in the German patent application DE 9 38 566 proposed acetylsalicylic acid before First compress in granulate form, gently but completely dry and then coated with finely divided silica. Then you can with highly disperse silica powdered acetylsalicylic acid granules with others Tablet ingredients, which may be in powder or granular form, mixed and compressed into tablets. The interface of highly disperse Silicic acid acts not only as an insulating layer and protection against unwanted reactions, but also it also contributes to the rapid disintegration of the tablets even after a long storage period.

German patent application DE 12 28 029 describes the production of tablets, where powder mixtures without prior granulation first with cellulose powder and optionally mixed silica, according to a preferred Embodiment are ground and then pressed.

From the German patent application DE 41 21 127 in turn shows that a particularly good auxiliary in the manufacture of pharmaceutical tablets cellulose particles has, on the surface of which a lamination is fixed. The excipient is in as possible finely divided form used; where average particle sizes of below 200 microns as can be represented particularly advantageously. Usually the classic Tablet disintegrant of the first class of substances mentioned in very fine-particle form either before pressing with the other tablet ingredients that are finely divided or can be present in granular form, mixed or the other tablet ingredients are added coated or powdered the tablet disintegrant.

In the field of detergents or cleaning agents, according to the teaching of the European the patent EP-B-0 523 099, the disintegrants used by the Arz Neimittelfertigung ago are known. Swellable ones are mentioned as disintegrants Layered silicates such as bentonites, natural substances and natural substance derivatives on starch and cellulose Base, alginates and the like, potato starch, methyl cellulose and / or hydroxypropyl  cellulose. These disintegrants can be mixed with the granules to be pressed, however already incorporated into the granules to be pressed.

International patent application WO-A-96/06156 also states that the installation of Disintegrants in detergent or cleaning agent tablets can be advantageous. In turn microcrystalline cellulose, sugar such as sorbitol, but also as typical disintegrants Layered silicates, especially finely divided and swellable layered silicates of the type Called bentonites and smectites. Substances that contribute to gas formation, such as Citro Nenoic acid, bisulfate, bicarbonate, carbonate and percarbonate are considered possible decay tools listed.

In 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 Ta described bletten, whereby compacted particulate material with a particle size between between 180 and 2000 µm is used. The resulting tablets can be either have homogeneous as well as a heterogeneous structure. According to EP-A-0 522 766 at least the particles containing surfactants and builders with a solution or dis persion of a binder / disintegrant, in particular polyethylene glycol. Other Binder / disintegration aids are in turn those which have already been described and known several times Disintegrants, for example starches and starch derivatives, commercially available cellulose Derivatives such as cross-linked and modified cellulose, microcrystalline cellulose fibers, cross-linked polyvinylpyrrolidones, layered silicates etc. Also weak acids like Citro Nenoic acid or tartaric acid, which in connection with carbonate-containing sources in the Contact with water leads to effervescent effects and according to the Römpp definition the second class of explosives can be used as a coating material.

Particular reference is made to the non-prepublished DE 197 10 254, the explosives describes whose particle size distribution (sieve analysis) is designed such that maximum 1% by weight, preferably less, of dust components and total (including of any dust present) less than 10% by weight of the disintegrant granules are smaller than 0.2 mm. Advantageously, at least 90% by weight of the Disintegrant granules 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.

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 body, the dissolution time is of the entire molded body preferably shorter than the duration of the main wash cycle  conventional dishwasher, i.e. shorter than 40 minutes, particularly preferably shorter than 30 min, very particularly preferably shorter than 20 min and extremely preferably shorter than 10 min.

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

If a component for delayed release is included, one is preferred Embodiment longer the dissolution time of the entire molded body in 20 ° C cold water than the pre-wash cycle of a standard dishwasher, i.e. longer than 5 minutes, preferably longer than 10 min.

General forms of presentation

All possible three-dimensional bodies are suitable for the spatial shape of the shaped body, how u. a. in the prior art patents and the standard works of Technical literature (eg: Riedel, "Die Tablette") but also in the patent documents of the state of the art Technology are enumerated. The area in which the ingredient (I) is contained is also not tied to a specific spatial shape. Is preferred for practical reasons however, an expansion in a spatial direction of more than 5 mm.

Specific forms of presentation

In a preferred embodiment of the invention, homogeneous or heterogeneous Shaped body of known design provided.

These include, in particular, cylindrical tablets, these tablets preferably have a diameter of 15 to 60 mm, in particular 30 +/- 10 mm. The height this tablet 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. In special designs, the height is 24, 25, 26, 27 or 28 mm.

But also square, rectangular, trapezoidal, oval and irregularly shaped Base areas can be used preferentially. The edge lengths are preferred between 15 to 60 mm, in particular from 30 +/- 10 mm.

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

Depending on the type of application, the water hardness range or the pollution, 1 or more, for example 2 to 4 tablets, in particular tablets become. Other 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 shaped body are homogeneously distributed except for the area with ingredient (I), that with the naked eye no different ingredients and / or active ingredients are perceptible. Of course, the grain structure of the solids used can still be recognizable. In a preferred embodiment of the invention, in addition to the Area with the ingredient (I) only one further area (phase) available.

Accordingly, heterogeneous shaped bodies are understood to mean those which do not to have a homogeneous distribution of the ingredients present in addition to the ingredient (I) to have. In a simple case, heterogeneous shaped bodies can, for example, do this be made that the different ingredients have different colors and / or wear a different fragrance component.

Another case of the non-uniform (heterogeneous) shaped bodies according to the invention to count, includes an embodiment in which a molded body is pressed, the In addition to the area with the ingredient (I), several layers (phases), i.e. at least has two layers. It is e.g. B. possible that these different layers un have different disintegration and dissolution rates and / or different Wear ingredients. This can result in advantageous application properties of the Moldings result. If, for example, ingredients are contained in the shaped bodies, that mutually influence each other negatively, so it is possible to separate them. Should be in one It is so that a defined sequence of cleaning conditions can be created on the machine possible, the one (or more) component (s) in one (or the) faster disintegrating and / or to integrate more quickly soluble layer and the other component (s) in one (or the slower disintegrating layer (s) so that a component with Lead time may have an effect or has already reacted if another goes into solution.

A preferred embodiment of the invention is that in addition to the area with the ingredient (I) has two more phases. It is particularly favorable if the volume ratios of the two further phases between 10: 1 and 1:10, preferred between 5: 1 and 1: 5, particularly preferably between 2: 1 and 1: 2.

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

The layer structure of the moldings can be stacked, with one solder process of the inner layer (s) at the edges of the molded body already takes place,  if the outer layers have not yet completely dissolved or disintegrated; but it can also a complete and / or partial covering of the inner layer (s) by the layers lying further out can be achieved, which leads to prevention and / or Delaying the early release of components of the inner layer (s) leads.

In a further preferred embodiment of the invention, a tablet consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while at the two top layers of the stacked tablet and the cover-shaped tablet however, the outermost layers are free of peroxy bleach. It is also possible Peroxy bleach and any bleach activators or bleach catalysts present to separate gates and / or enzymes spatially in a tablet / tablet nen. Such configurations have the advantage that in the inventive Shaped bodies would have no fear of undesirable interactions.

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

The agents according to the invention are produced by the usual methods of Molded body manufacture.

In some embodiments, it has proven to be particularly advantageous to use the area the ingredient (s) in the form of a liquid (generally by solution and / or melt) optionally at elevated temperatures in a prefabricated  Fill in the recess of the surrounding ingredients and then by usual technical Measures to freeze this area (generally by drying and / or Cooling). This has a viscosity of more than 1500 mPas, preferably more than 2000 mPas, particularly preferably between 2000 and 15,000 mPas, very particularly preferred between 2500 and 7000 mPas and most preferably between 3000 and 4000 mPas especially proven.

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

Non-ionic surfactants are particularly suitable for the purposes of the present invention (Dehypon® LT 104, Dehypon® LS 54, Dehydol® LS 30, Lutensol® AT 80), Polyethylene glycols with different molecular weights (PEG 400, 12 000), soaps (Lorol® C 16), stearate (Cutina® GMS), but also thickened sodium hydroxide and meltable Salts such as sodium carbonate decahydrate. The advantages and disadvantages of each ingredient are to be understood by the expert on the basis of tests.

The use of mixtures as described in. Is particularly suitable for the present application the unpublished publication DE 197 27 073 is mentioned and its disclosure is hereby expressly included in this document.

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

A simple pressing of the components is also possible. In addition to Powders and granules also microtabs and moldings of smaller dimensions than that find final moldings.

Specific ingredients

Special ingredients (I) that are used in the context of the invention are Bleach activators. Known bleach activators are compounds that have one or more Contain N- or O-acyl groups, such as substances from the class of anhydrides, the esters, the Imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhexylene diamine TAHD, but also Pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and Isatoic anhydride ISA.

As bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acid are used  become. Suitable substances are the O- and / or N-acyl groups of the named C number of carbon atoms and / or optionally substituted benzoyl groups. Are preferred polyacylated alkylenediamines, especially 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, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, Ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well as acetylated sorbitol and mannitol as their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), penta acetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, if necessary N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which is derived 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 known from German patent application DE 196 16 769 Acylacetale and those in German patent application DE 196 16 770 and the international patent application WO 95/14075 described acyllactams also preferably used. Also from the German patent application DE 44 43 177 known combinations of conventional bleach activators can be used. Such bleach activators are in the usual range of amounts, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total Means included.

In addition to the conventional bleach activators listed above or in their place can also be those from European patents EP 0 446 982 and EP 0 453 003 knew sulfonimines and / or bleach-enhancing transition metal salts respectively Transition metal complexes can be included as so-called bleaching catalysts. To the in Transition metal compounds in question include in particular those from the German patent application DE 195 29 905 known manganese, iron, cobalt, Ruthenium or molybdenum salt complexes and those from the German patent application DE 196 20 267 known N-analog compounds, which are from the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum Carbonyl complexes described in German patent application DE 196 05 688 Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, from the German patent application  DE 196 20 411 known cobalt, iron, copper and ruthenium amine complexes, which in the German patent application DE 44 16 438 described manganese, copper and cobalt Complexes described in European patent application EP 0 272 030 Complexes known from the European patent application EP 0 693 550 manganese Complexes known from the European patent EP 0 392 592 manganese, iron, Cobalt and copper complexes and / or those in European Patent EP 0 443 651 or European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, Manganese complexes described in EP 0 549 272, EP 0 544 490 and EP 0 544 519. Combinations of bleach activators and transition metal bleach catalysts are for example from German patent application DE 196 13 103 and international Patent application WO 95/27775 known. Bleach activators from the Group of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), MMA, preferably in amounts 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 all the means used.

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

Special ingredients (I) which are used in the context of the invention are substances which which prevent re-soiling of surfaces and / or dirt separation facilitate after a single application (so-called "soil release connections").

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. As particularly suitable  cationic polymers are hydroxypropyltrimethylammonium guar, copolymers of Aminoethyl methacrylate and acrylamide as well as copolymers of dimethyldiallyl described ammonium chloride and acrylamide.

EP-A-0 342 997 describes all-purpose cleaners, the cationic polymers may contain, in particular polymers with imino groups are used.

DE-OS-26 16 404 describes cleaning agents for glass, the cationic Contain cellulose derivatives. The addition of the cationic cellulose derivatives in the agents better drainage of the water to get streak-free cleaned glass.

In EP-A-0 467 472 e.g. B. Hard surface cleaners are described contain cationic homo- and / or copolymers as soil-release polymers. This Polymers have quaternized ammonium alkyl methacrylate groups as monomer units. These compounds are used to equip the surfaces so that when the next time you clean it, the dirt can be removed more easily.

The cationic polymers are particularly preferably selected from cationic Polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or -acrylamide; Dialkyldiallyldiammonium 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 Page groups as soil release connections.

In the context of this application, natural ones are also exceptionally preferred Polyuronic acids and related substances, as well as polyampholytes and hydrophobized Polyampholytes, or mixtures of these substances.

According to the invention, between 0 and 5% by weight of enzymes can be obtained from the cleaning agent be added to the entire preparation to improve the performance of the detergent increase or under milder conditions the cleaning performance of the same quality guarantee. 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 Novo Nordisk. Duramyl® and Termamyl® are particularly used as amylases 60 T, and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades. Other enzymes can also be used.  

Special ingredients (I) that are used in the context of the invention are Oxygen bleach, preferably the alkali metal perborates and their hydrates and Alkali metal percarbonates, in the context of the invention preferably sodium perborate as Mono- or tetrahydrate, or sodium percarbonate and their hydrates are used. The persulphates can also be used.

Typical oxygen bleaches are also organic peracids. To the preferably used organic peracids, especially the excellently effective Phthalimidoperoxycaproic acid, but also all other known peracids are in principle usable.

Dishwashing detergents according to the invention can be used as ingredient (I) to protect the dishes or the machine contain corrosion inhibitors, silver protection agents in particular Machine dishwashing have a special meaning. Can be used are the known substances of the prior art, such as. B. in DE 43 25 922, the DE 41 28 672 or DE 43 38 724 described. Generally, above all Silver preservatives selected from the group of triazoles, benzotriazoles, Bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole are particularly preferred and / or alkylaminotriazole. You will also often find it in detergent formulations agents containing active chlorine, which can significantly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex find inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce frequent use. The transition metal salts that are selected are preferred here from the group of manganese and / or cobalt salts and / or complexes, especially before moves the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, chlorides of cobalt or manganese and manganese sulfate. Likewise Zinc compounds can be used to prevent corrosion on the wash ware.

Other ingredients

All of the ingredients described above can be used in the moldings according to the invention (I) also take on the function of other ingredients, should the condition of range of other ingredients are met.

Water-soluble and water-insoluble can be used in the cleaning agents according to the invention Builder are mainly used to bind calcium and magnesium. Are there Water-soluble builders preferred because they usually appear on dishes and hard surfaces  less tend to form insoluble residues. Usual builder in the frame the invention present between 10 and 90% by weight, based on the entire preparation may be 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 also can be used, as well as mixtures of the aforementioned builder substances.

Trisodium citrate and / or pentasodium tripolyphosphate and / or are preferred Sodium carbonate and / or sodium bicarbonate and / or gluconate and / or silicate Builder from the class of disilicate and / or metasilicate used.

Alkali carriers can be present as further constituents. Are considered to be alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metasilicates, and mixtures of the aforementioned substances, in the sense of this invention, the alkali carbonates, in particular sodium, are preferred carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can be used.

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

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

In principle, all surfactants can be used as surfactants. The nonionic are preferred Surfactants and especially the low-foaming non-ionic surfactants, but also other low-foaming surfactants are possible. Those are particularly preferred alkoxylated alcohols, especially the ethoxylated and / or propoxylated, the Alkyl polyglycosides and the alkyl polyglucamides.

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 context of the present invention the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₈ , such as C ₁₁ -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. Another 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 for the purposes of the invention. Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

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

Fatty acid polyhydroxylamides (glucamides) are acylated reaction products of the reductive amination of a sugar (glucose) with ammonia, generally long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid chlorides are 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 of C ₆ to C ₁₂ 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 shaped body are different in the shaped body are colored. In a special embodiment of the shaped body, the color is red Another special design of the molded body is the color green. In another The special design of the molded body is yellow. In another special Design of the molded body, the color is a mixture of different colors.

The storage stability of the shaped body is particularly important. It is according to the invention particularly preferred if the weight gain of the area contributes to the ingredient (I) Storage under normal household conditions, d. H. between 15 and 30 ° C and between 5 and 55% humidity, preferably 15 and 35% 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 very preferably not more than 10% by weight is at best not more than 5% by weight.

It is also particularly preferred according to the invention if the loss occurs Active ingredient of ingredient (I) when stored under normal household conditions, d. H. between 15 and 30 ° C and between 5 and 55% humidity, preferably 15 and 35% Air humidity for a period of 30 days, preferably 60 days, particularly preferably 90 Days not more than 50 wt .-%, preferably not more than 40 wt .-%, 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 is.

It is also particularly preferred according to the invention if the absorption maximum a 1% solution of a colored area or component  Storage under normal household conditions, d. H. between 15 and 30 ° C and between 5 and 55% humidity, preferably 15 and 35% humidity for a period of 30 Days, preferably 60 days, particularly preferably 90 days, not more than 100 Wavenumbers, preferably not more than 50 wavenumbers, very particularly preferably not more than 30 wavenumbers, most preferably not more than 20 wavenumbers and most preferably not more than 10 wave numbers, at best not more than 5 Wavenumbers is.  

Examples

The following recipes were mixed and pressed into shaped bodies. The one in brackets specified ingredients are examples of the substance class but can be replaced by others in the Registration enumerated substances will be replaced. The frame formulations represent preferred Fields of the invention.

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

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

The builder system of the above frame recipe 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 test formulation (V) was used:

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

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

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

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

The following can be used as the basic formulation (R) for the present application (data in% by 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 body according to the invention, it can each formulation is also part of a single phase, d. H. get the shares then not as usual on the overall recipe, but on the composition of the single phase.

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

The production of the moldings according to the invention uses steps that the knowledge of Are known to those skilled in the art in other contexts. A preferred one Embodiment of the molded body of the first claim contains a trough in one Tablet, this well containing the ingredient (I) (bleach activator). The production happens in a preferred case so that you emboss a recess in a molded body and filled this depression. The embossing can be done on a rotary press from Korsch respectively. In the present case, a tablet press from Fette was used. A Round tablet shape (26 × 36 mm) was chosen and with a stamp 5 mm deep on one Side embossed, the base area was chosen so that a volume of 1 ml is filled and the tablet had a smooth surface afterwards.

A liquid mixture of paraffin and an active ingredient (I) was then introduced and let cool down. This cooling can be supported by common apparatus methods become.  

As already mentioned, the ingredient (I) was inventively in the corresponding Re formula that surrounds the filled area, previously reduced in quantity and in the existing examples and studies in the surrounding areas are omitted.

In comparative experiments with homogeneous (noninventive ingredient (I)) and some Commercial tablets proved to be superior to the tablets according to the invention.

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

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

In addition, the special properties of the agents according to the invention by tech nisch untrained people under practical conditions compared to homoge checked tablets. It was out of tips for dosage and general Safety instructions have no influence on the handling of funds by the group of people in commercial dishwashers. This attempt to compare failed looks particularly good. The cleaning results were rated as particularly favorable here.

The results with a bleach activator as active ingredient (I) were in a conventional 55 ° C wash program achieved.

In a mixture according to the formula Ra or Va1, independently of one another, up to to 20 wt .-% and in one case n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) in in another case, TAED is used as the bleach activator component.

In a further washing test, samples (according to Ra), the small amounts of metal catalysts 0.25% by weight (in each case several different Mn catalysts,
but especially cobalt catalyst, specifically the cobalt pentamine chloro complex) contained once in a homogeneous distribution in the tablet and once 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 the area (I), which was a hollow in the present case.

The effect becomes even clearer when using a mixture of activator components and paraffin in a standard program at 55 ° C. The cleaning results were already  better immediately after production. The effect increased with storage. Especially tea shows improvements here, but also in milk, burnt-in meat, burned-in meat Meat, egg and starch mixtures showed better cleaning performance than with mold bodies 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. Off The effect is more pronounced in paraffins with a melting point of 46-48 ° C. Also strong too you can see the cleaning effect on paraffins with a melting point of 57-60 ° C.

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

The results clearly show that the agents according to the invention are standard dishwashing medium tablets are superior.

Claims (33)

1. Shaped body containing builders, alkali carriers, bleaches, enzymes and surfactants, characterized in that in an area not greater than 40 vol .-%, more than 80 wt .-%, an active ingredient (I) with a component from the group of Bleach activators is included. 2. Shaped body according to claim 1, characterized in that the area between 1 and 30 vol .-%, particularly preferably between 2 and 25 vol .-%, very particularly preferred between 3 and 20 vol .-% of the shaped body more than 90 wt .-%, particularly preferred more than 95% by weight, very particularly preferably the total amount of one present Ingredient (I) is included. 3. Shaped body according to claim 1, characterized in that this ingredient (I) Mixture of bleach activator and / or bleach from the group of chlorine and / or Oxygen bleach and / or silver protectant and / or enzyme and / or soil Release connection and / or a component for solubility control and / or other ingredients. 4. Shaped body according to one of the preceding claims, characterized in that at least one oxygen bleaching agent selected from the group of alkali perborates, Alkali percarbonates, which contain organic peracids and hydrogen peroxide. 5. Shaped body according to one of the preceding claims, characterized in that the Ingredient (I) 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 higher molecular weight Contains polyethylene glycols. 6. Shaped body according to one of the preceding claims, characterized in that a Bleach activator, preferably from the group of multi-acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), MMA and / or 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, of manganese sulfate, preferably in quantities from 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on total means is included.   7. Shaped body according to one of the preceding claims, characterized in that furthermore one or more builders from the group of the gluconates, the low molecular weight Polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarbonate acids and their salts, the 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 Disilicate and / or metasilicate is used. 8. Shaped body according to one of the preceding claims, characterized in that as Builder system includes a mixture of tripolyphosphate and sodium carbonate. 9. Shaped body according to one of the preceding claims, characterized in that as Buildersystem is a mixture of tripolyphosphate and sodium carbonate Contains sodium disilicate. 10. Shaped 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, most preferably the alkoxylated and / or propoxylated fatty alcohols, the alkyl polyglycosides, the Alkyl polyglucamides and / or mixtures of the above surfactants. 11. Shaped body according to one of the preceding claims, characterized in that additionally at least one silver protection agent selected from the group of triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes is contained. 12. Shaped body according to claim 11, characterized in that as a silver protective agent Benzotriazole and / or alkylaminotriazole is included. 13. Shaped body according to claim 11, characterized in that the transition metal salts 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. 14. Shaped 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, microwaxes and high molecular weight polyethylene glycols are included. 15. Shaped body according to claim 14, characterized in that the dissolution time of the entire molded body is longer than the duration of the pre-rinse cycle of a conventional Dishwasher.   16. Shaped 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 Citric acid / bicarbonate and / or the celluloses and cellulose derivatives are contained. 17. Shaped body according to claim 16, characterized in that the dissolution time of the entire molded body is shorter than the duration of the main wash cycle conventional dishwasher. 18. Shaped body according to one of the preceding claims, characterized in that only yet another area or phase is included. 19. Shaped body according to one of claims 1-17, characterized in that two more Areas or phases are available. 20. Shaped body according to claim 19, characterized in that the volume ratios the other two phases between 10: 1 and 1:10, preferably between 5: 1 and 1: 5, are particularly preferably between 2: 1 and 1: 2. 21. Shaped body according to one of claims 1-17, characterized in that three or more more phases are available. 22. Shaped body according to one of the preceding claims, characterized in that one or the bleaching component, especially the chlorine component, not in one Phase is assembled together with the perfume component. 23. Shaped body according to one of the preceding claims, characterized in that the Silver protection component not assembled with one or more of the bleaching components becomes. 24. Shaped body according to one of the preceding claims, characterized in that one or the component for solubility control together with the Bleach activator is made up. 25. Shaped body according to one of the preceding claims, characterized in that one of the component or components for solubility control together with the enzymes is assembled. 26. Shaped body according to one of the preceding claims, characterized in that one of the component or components for solubility control together with the bleach is assembled. 27. Shaped body according to one of the preceding claims, characterized in that one of the component or components for solubility control together with the Silver protection component is assembled.   28. Shaped 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% by weight, preferably more than 70% by weight, particularly more than 90% by weight of a surfactant or the total surfactant mixture is made up. 29. Shaped body according to one of the preceding claims, characterized in that one or more or all areas of the molded body are colored differently. 30. Shaped body according to one of the preceding claims, characterized in that a color is red. 31. Shaped body according to one of the preceding claims, characterized in that a color is green. 32. Shaped body according to one of the preceding claims, characterized in that a color is yellow. 33. Shaped body according to one of the preceding claims, characterized in that the Color is a mixture of different colors.