WO1999035235A1

WO1999035235A1 - Shaped bodies of dishwashing detergent with chlorine bleaching agents

Info

Publication number: WO1999035235A1
Application number: PCT/EP1998/008372
Authority: WO
Inventors: Jürgen Härer; Thomas Otto Gassenmeier; Christian Nitsch; Hans-Josef Beaujean; Bernd Richter; Thomas Möller
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1997-12-30
Filing date: 1998-12-21
Publication date: 1999-07-15
Also published as: PL341351A1; JP2002500271A; EP1044258A1; DE19758178A1; SK10052000A3; HUP0101379A2; CZ20002495A3; CA2298105A1

Abstract

The invention relates to shaped bodies containing builder substances, alkali supports, bleaching agents, enzymes and tensides. The inventive shaped bodies are highly effective, highly stable in storage, have a pleasant fragrance and a defined solubility profile. An area making up not more than 40 vol. % of the shaped body contains more than 80 wt. % of the total content of an active substance I contained in the shaped body with a constituent from the group of chlorine bleaching agents and a meltable constituent for checking solubility from the group of tensides, paraffins, micro waxes and higher molecular polyethylene glycols.

Description

Dishwashing tablets with chlorine bleach

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 powdery agents, such as advantageous handling, simple metering, and low packaging volume requirements.

Problems arise, however, in that relatively high compression pressures have to be used to achieve adequate dimensional stability and fracture resistance when pressing 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 of the prior art patents are said to avoid some of these problems.

However, the consumer is often unable to understand the performance advantages described there. Therefore, an important problem for suppliers of shaped articles that are active in washing or cleaning is to satisfy consumers.

It was therefore an object of the present invention to provide high-performance, easy-to-handle washing or cleaning-active moldings, in particular dishwasher tablets, detergent tablets, stain remover tablets or water softening tablets for use in the home, in particular for machine use with high storage stability, low To provide packaging effort, a good fragrance profile and a defined solubility profile, which above all result in high customer satisfaction.

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

The application therefore relates to a molded article containing builder substances, alkali carriers, bleaching agents, enzymes and surfactants, characterized in that in a range of not more than 40% by volume, more than 80% by weight, of a mixture of active substance (I) Bleaching agent from the group of chlorine bleaching agents and a fusible component for solubility control selected from the group of surfactants, paraffins, microwaxes, higher molecular weight polyethylene glycols.

In addition to the bleaching agent from the group of chlorine bleaching agents, the ingredient (I) can also be a bleach activator, a silver protection agent 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 and at least one other ingredient from the group consisting of bleach and / or bleach activator and / or silver protective 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 compression 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 in exactly three spatial directions is surrounded by other ingredients of the molded body.

It is also preferred in the context 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 an In present - The substance (I) is present, which dissolves faster than the and / or the by 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% 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 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 ingredient (I) present.

A desirable effect on the overall result can also be obtained if the weight gain of the area with 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 effect 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% atmospheric 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, entirely 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, Dextrans, cross-linked polyvinylpyrrolidones and others; systems made from weak acids and agents containing carbonate, in particular citric acid and tartaric acid in combination with bicarbonate or carbonate and also 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.

European patent applications EP-A-0 466485, 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 active cleaning tablets, using compact, particulate material with a particle size between 180 and 2000 μm. The resulting tablets can both have a homogeneous as well as 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 which have already been described 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, they lead to effervescent effects and, according to the definition according to Römpp, belong to the second class of disintegrants. They can be used as coating materials.

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 which contain disintegrants in granular or, if appropriate, cogranulated form are also described in German patent applications DE 197 09 991 (Stefan Herzog) and in 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 and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in 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 a detergent is contained in the molded body, the dissolution time of the entire molded body is preferably shorter than the duration of the main wash cycle of a conventional dishwasher, i.e. shorter than 40 min, particularly preferably shorter than 30 min, very particularly preferably shorter than 20 min and extremely preferably shorter than 10 min.

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, in a preferred embodiment the dissolution time of the entire molded body in 20 ° C. cold water is longer than the pre-rinse cycle of a commercially available dishwasher, that is to say longer than 5 min, preferably longer than 10 min.

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 moldings 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. 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 moldings, in particular the tablets, is preferably 15 to 60 g and in particular 20 to 40 g per molded body 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 level of contamination, 1 or more, for example 2 to 4, moldings, 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) shaped 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. For example, if ingredients in the form bodies are included, which mutually influence each other negatively, so it is possible to separate them. If a defined sequence of cleaning conditions is to be created in a machine, it is possible to integrate one (or more) component (s) in a (or) the more rapidly disintegrating and / or more quickly soluble layer and the other (n) component Incorporate into one or more slowly disintegrating layers so that one component can act with a lead time or has already reacted if another component 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, a complete and / or partial covering of the inner layer (s) can also be achieved by the layers lying further outwards, 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 stack-like tablet the two outer layers and in the case of the shell-like one 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 in one phase is made up together with the perfume component. Another cheap and preferred embodiment of the invention consists in that the silver protection component is not made up with one 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 is 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 all of them - is mixed.

The agents according to the invention are produced by the customary 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. A manufacturing process for such shaped bodies filled with melt dispersions or emulsions is disclosed in German patent application DE 198 31 704.2 (Henkel KGaA). A process for the production of coated particles, in particular coated particles of chlorine bleach, is also described in German patent application DE 197 27 073.5 (Henkel KGaA). The redesigned according to the teaching of this document Enveloped particles can be pressed or pressed directly onto or in molded bodies, or melted and filled into depressions.

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), 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. Waxes are particularly preferred as meltable components in the context of the present invention. "Waxing" is understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C. without decomposition and which are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes. Synthetic waxes are generally understood to be polyacetylene waxes or polyalkylene glycol waxes.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with more than 28 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol) or melissyl alcohol. The fusible component can optionally also contain wool wax alcohols, which means trite phene and steroid alcohols, for example lanolin. In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides but also, if appropriate, water-insoluble or only slightly water-soluble polyalkylene glycol compounds can likewise be used at least in part as part of the meltable component.

Most of the meltable component preferably contains paraffin wax. This means that at least 50% by weight of the meltable component, preferably more, consists of paraffin wax. Paraffin wax contents in the coating of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred. In a special embodiment of the invention, the fusible component consists exclusively of paraffin wax.

Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that there is no hydrolysis of the waxes in an alkaline detergent environment (as is to be expected, for example, from the wax esters), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C, particularly preferably of more than 60 ° C. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if the melting temperature in the detergent solution drops below this. Such wax residues usually lead to an unsightly appearance on the cleaned surface and should therefore be avoided. The coating according to the invention preferably contains at least one paraffin wax with a melting point of about 57 ° C. to about 60 ° C.

Preferably, the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally about 10 to about 30 ° C.) is as high as possible. The more solid wax components present in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing proportion of solid wax components, the resilience of the coating to impacts or friction on other surfaces increases, which leads to a longer-lasting protection of the coated particles. High proportions of oils or liquid wax components can weaken the coating, opening pores and exposing the particles made up with the meltable component to the environmental influences mentioned at the beginning.

At unusually low temperatures, for example at temperatures below 0 ° C, the solidified, meltable component can break under impact or friction. In order to improve the stability at such low temperatures, additives can optionally be added to the fusible component. Suitable additives must be able to be mixed completely with the molten wax, must not significantly change the melting range of the coating, must improve the elasticity of the solidified fusible component at low temperatures, must not and must not generally increase the permeability of the solidified fusible component to water or moisture do not increase the viscosity of the melt of the coating material to such an extent that processing becomes difficult or even impossible. - Suitable additives which reduce the brittleness of a coating consisting essentially of paraffin at depth Lowering temperatures are, for example, EVA copolymers, hydrogenated resin acid methyl ester, polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.

In addition to paraffin, the fusible component can also contain one or more of the above-mentioned waxes or wax-like substances as the main constituent. In principle, the mixture forming the cover should be such that the cover is at least largely water-insoluble. The solubility in water should not exceed about 10 mg / 1 at a temperature of about 30 ° C. and should preferably be below 5 mg / 1.

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.

Ingredients:

Special ingredients (I) which are additionally used in the context of the invention are substances which prevent 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 trialkylammomumalkyl (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 side groups as soil release compounds.

Natural polyuronic acids and related substances, as well as polyampholytes and hydrophobized polyampholytes, or mixtures of these substances, are also exceptionally preferred in the context of this application.

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 Bio- zym, 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.

Other ingredients:

Particular ingredients 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 the 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.

Special ingredients that are used in the context of the invention are bleach activators. Known bleach activators are compounds that 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, tetraacetylmethylene diamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, l, 5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine DADHT and isatoic acid anhydride ISA.

Compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used as bleach activators. 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. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated tria- Zinderivate, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-Moφholinium Acetonitrile methyl sulfate (MMA), 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), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamin and Gluconolacton, and / or N-acylier te lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498. The hydrophilically substituted 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 0446 982 and EP 0 453 003 can also be present as so-called bleaching catalysts. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, the « Manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes known from German patent application DE 195 36 082, which are described in German patent application DE 196 05 688 wrote manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and. known from German patent application DE 196 20 411 Ruthenium-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 0693 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 0 458 397, EP 0 458 398, EP 0 549 271, 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 tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (NOBS) or isobenzene sulfonate (N-) iso , MMA, 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 Means used.

Bleach-boosting 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 cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight. % to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total composition. But in special cases, more bleach activator can be used.

Dishwashing detergents according to the invention may contain corrosion inhibitors as ingredients for protecting the wash ware or the machine, with particular protection agents being of particular importance in the field of automatic dishwashing. The known subsets of the prior art, such as. B. in DE 43 25 922, the DE 41 28 672 or DE 43 38 724 described. In general, silver protection agents selected from the group consisting of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. According to the above documents, 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. 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.

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 builder substances.

Are 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 _c of disilicates and / or metasilicates. Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances are considered to be alkali carriers, alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium quartz carbonate 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 alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols (Cio to C ₁₈ , preferably between C ₁ and C ₁₆ , such as Cn-, C ₁₂ -, C ₁₃ -, C ₁ -, Cj ₅ -, C ₁₆ -, C ₁ - and C ₁₈ -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 substance class of the “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 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 polyglucosi- de, wherein the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-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, 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 is described. 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 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 weight increase in the area of the ingredient (I) when stored under normal household conditions, ie. 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.

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% atmospheric humidity, preferably 15 and 35% Humidity for a period 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 wavenumbers, at best not more than 5 wavenumbers.

Examples

The following recipes were mixed and pressed into shaped bodies. 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):

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):

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

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

%):

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 formulation can also be the constituents of an individual phase, ie 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 commonly used 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 trough in a tablet, this trough containing the chlorine bleaching ingredient (I). In a preferred case, the production takes place in such a way that a depression is embossed into a molded body and this depression is filled. The embossing can be done on a Korsch rotary press. 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 compared with known agents using the example of tea cleaning. The special properties of the agents according to the invention were tested in comparison to known agents 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. In addition to instructions for the dosage and general my safety instructions have no influence on the handling of the funds 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.

In an experiment, samples according to the general formulation Ra which contained active chlorine (dichlorocyanate) as bleaching component were used once in a homogeneous distribution in the tablet and once according to claim 1, so that the active chlorine was largely separated from other (especially enzyme-containing) components. The storage stability after two weeks was significantly worse in the case of the homogeneous tablet, so that no satisfactory cleaning effect on milk and more soiling was found. This applies to the normal assembly of the bleaching component in area (I), which in the present case represented a hollow. The effect becomes even clearer when using a mixture of chlorine component and paraffin in a standard program at 55 ° C. The cleaning results were better immediately after production. The effect increased with storage. In particular, tea, milk, burnt-on meat, burned-in meat, egg and starch mixtures showed significantly better cleaning performance than molded articles without area with the ingredient (I), with homogeneously distributed component (I) and some 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 is special for paraffins with a melting point of 57-60 ° C.

The results clearly show that the agents according to the invention are superior to conventional dishwasher tablets.

In further examples, melt dispersions of dichloroisocyanuric acid (DICA) were produced in coating substances, which demonstrate the positive effects. 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 shell material and stirring in the solid active substance (DICA), melt dispersions SDE 1 and 2 were produced, the composition (% by weight, based on the melt) of which is given in the table below:

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

According to the teaching of German patent application DE 198 31 704.2, the melt dispersions were introduced into the moldings and allowed to cool. Here, the shaped bodies 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 and E2 filled with the melt dispersions SDE 1 and SDE 2 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 detergents for the soiling of tea according to the instructions under (1) was carried out visually by experts and graded, the rating "0" meaning no cleaning on a scale of 0-10 and "10" meaning complete removal of the stains. The teen notes were measured both for washing conditions 55 ° C / 16 ° d water hardness in the main rinse cycle (i.e. "hard conditions") and for 55 ° C / 3 ° d water hardness. A Miele G 590 with a universal program was used as the dishwasher. The table below shows the achieved tea cleaning of agents El and E2 compared to an unfilled molded article V

The results show that the molded bodies E1 and E2 according to the invention are far superior to the comparison molded body V when cleaning tea.

In another example, according to the teaching of German patent application DE 197 27 073.5, dichloroisocyanuric acid (DICA) was embedded in paraffin according to the following recipe: DICA 35% by weight

Tylose MH 50 15% by weight

Paraffin (57-60 ° C) 50% by weight

1.3 g of the bleaching agent coated in this way were sprinkled into the cavity of the shaped bodies described above and pressed into a solid core. The cleaning performance of the molded body E3 produced in this way was 10.0 (3 ° dH) or 8.5 (16 ° dH) according to the above test conditions.

Claims

Claims:

1. Shaped body containing builders, alkali carriers, bleaches, enzymes and surfactants, characterized in that in a range not greater than 40 vol .-%, more than 80 wt .-%, a mixture of active substance (I) a bleaching agent from the group the chlorine bleach and a meltable component for solubility control selected from the group of surfactants, paraffins, microwaxes, higher molecular weight polyethylene glycols.

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 body according to claim 1, characterized in that this ingredient (I) is a mixture of bleach from the group of chlorine bleach and another ingredient from the group of bleach activator and / or silver protection agent and / or enzyme and / or a component for solubility control and / or other ingredients.

4. molded article according to one of the preceding claims, characterized in that at least one bleaching agent selected from the group consisting of trichlocyanuric acids, dichloro- or monochlorocyanurates, hypochlorites, and other conventional chlorine-containing bleaching agents is contained.

5. Molded body according to one of the preceding claims, characterized in that the fusible component is a paraffin.

6. molded article according to claim 5, characterized in that the paraffin has a melting point of more than 40-44 ° C, preferably more than 46-48 ° C, particularly preferably between 57-60 ° C.

7. Molded body according to 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 polycar- bonic 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.

8. Molded body according to one of the preceding claims, characterized in that a mixture of tripolyphosphate and / or sodium carbonate and / or sodium disilicate is included as the builder system.

9. 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.

10. Molded body according to one of the preceding claims, characterized in that additionally contain 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, preferably benzotriazole and or alkylaminotriazole is.

11. Shaped body according to claim 10, 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.

12. 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.

13. 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.

14. Molded body according to one of the preceding claims, characterized in that one or more of the bleaching components, especially the chlorine component, is not assembled in one phase with the perfume component.

15. 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.

16. 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.

17. 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.

18. 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.

19. 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.

20. 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.