SK9992000A3 - Moulded body containing activating agents, alkali carriers, bleaching agents and enzymes, and use thereof - Google Patents

Abstract

The present invention relates to moulded bodies containing builder substances, alkali carriers, bleaching agents, enzymes and surfactants. Particularly powerful moulded bodies with a high degree of storage stability, a good scent profile and a defined solubility profile are obtained when an area corresponding to no more than 40 vol. % of the moulded body contains more than 80 wt. % of the total amount of an active substance (I) contained in the moulded body with an ingredient from the group of surfactants.

Description

Technical field

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

BACKGROUND OF THE INVENTION

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

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

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

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

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide high performance, easy to handle laundry detergent or cleaning detergent moldings, in particular dishwashing detergent tablets, laundry detergent tablets, stain removers tablets or water hardness tablets for domestic use, particularly for machine applications with high stability. storage, low packaging costs, good fragrance profile and defined solubility profile, which in particular guarantee high customer satisfaction.

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

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention provides a molded article which contains activating agents, alkalinity sources, bleaching agents and enzymes and which contains more than 80% by weight in a space not exceeding 40% by volume. of the active substance (I) containing a surfactant component.

In addition to the surfactant, the active ingredient (I) may contain at least one bleaching agent from the group of oxygen or chlorine bleaching agents, a bleach activator, a silver preservative and / or a soil release compound, an enzyme or a solubility control component or mixture. However, the active ingredient (I) may also be a mixture of several of these components.

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

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

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

Within the scope of the present invention, it is also preferred that there is at least one space with more than 80% by weight, more preferably with more than 90% by weight, particularly preferably with more than 95% by weight. and most preferably having a total active compound (I) content which dissolves by more than 5%, more preferably by more than 10%, particularly preferably by more than 25%, most preferably by more than 50% and in particular by more than 100% faster than the remaining spaces of the molded article.

It is also positive if the space with not more than 40% of the surface, more preferably between 5 and 30%, particularly preferably between 10 and 25%, most preferably between 15 and 20% by volume. The molded article contains more than 80 wt.%, more preferably more than 90 wt.%, particularly preferably more than 95 wt. and most preferably the total amount of active ingredient (I).

The desired effect on the overall result can also be achieved by providing a quantitative increase in the volume containing more than 80 wt. of the active ingredient (I) when stored under normal household conditions, i. between 15 and 30 ° C and between 5 and 55% air humidity, more preferably 15 and 35% air humidity for 30 days, more preferably 60 days, more preferably 90 days, not more than 50 wt%, more preferably not more than 40 wt% more preferably not more than 30% by weight, particularly preferably not more than 20% by weight, and particularly preferably not more than 10% by weight. % and most preferably not more than 5 wt.

The desired effect on the overall result can also be achieved in that the loss of the active ingredient (I) in the space containing more than 80 wt. the active ingredient when stored under normal household conditions, i. between 15 and 30 ° C and between 5 and 55% air humidity, more preferably 15 and 35% air humidity for 30 days, more preferably 60 days, more preferably 90 days, not more than 50 wt%, more preferably not more than 40 wt% very particularly preferably not more than 30% by weight, particularly preferably not more than 20% by weight. % and more preferably not more than 10 wt. % and most preferably not more than 5 wt.

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

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

solubility

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

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

The use of disintegrants is also found in the patent literature. Thus, it is proposed in German patent application DE 938 566 to first convert the acetylsalicylic acid into a granular form before pressing, gently but completely to dry and then to coat with highly disperse silicic acid. Subsequently, these acetylsalicylic acid granules powdered with highly dispersed silicic acid can be mixed and compressed into a tablet with other active ingredients of the tablet, which may be in powder or granular form. The high-dispersive silica separating layer not only acts as an insulating layer and protects against unwanted reactions, but also contributes to the rapid disintegration of the tablets even after prolonged storage.

German patent application DE 12 28 029 describes the production of tablets, wherein the powder mixtures are first mixed without prior granulation with cellulose powder and optionally with high dispersion silicic acid, more preferably ground and subsequently compressed.

It is again apparent from the German patent application DE 41 21 127 that a particularly good excipient in the manufacture of medicament tablets contains cellulose particles on the surface of which laminating agents are fixed. The excipient is used in the finest form possible; a mean particle size of less than 200 gm is particularly preferred. Typically, the conventional tablet disintegrants of the first class of substances in very fine-grained form are either mixed with the other active substances of the tablets, which may be in fine-grained or granulated form, before compression, or the other active substances of the tablets are coated or powdered.

In the field of detergents, according to the teaching of European patent EP-B-0 523 099, disintegrants known from the manufacture of medicaments can also be used. As disintegrating agents, swellable layered silicates such as bentonites, natural substances and derivatives of natural substances based on starch and cellulose, alginates and the like, potato starches, methylcellulose and / or hydroxypropylcellulose are mentioned. These disintegrants can be mixed with the granules to be pressed, but also incorporated into the granules to be pressed.

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

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

In particular, reference is made to the undisclosed DE 197 10 254 which discloses disintegrants having a particle size distribution (sieve analysis) that a maximum of 1% by weight, preferably less, is in the form of dust particles and less in total (including any dust particles present) % as 10 wt. The granulate disintegrant is less than 0.2 mm. Preferably, at least 90 wt. granulate disintegrant a particle size of at least 0.2 mm and at most 3 mm. These disintegrants are particularly suitable for the present invention.

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

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

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

-7General shapes

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

Specific embodiments

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

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

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

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

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

Homogeneous shaped articles are understood to be those in which the active substances of the shaped article are dispersed homogeneously to the active substance space (I) in such a way that the different active substances cannot be distinguished by the naked eye. Of course, the granulometric resolution can still be distinguished

-8Composition of used solids. In a more preferred embodiment of the invention there is only one space (phase) in addition to the active substance compartment (I).

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

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

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

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

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

In a further preferred embodiment of the invention, the tablet consists of at least three layers, i.e. two outer layers and at least one inner layer, wherein at least one of the inner layers comprises a peroxide bleaching agent, whereas in a stacked tablet both outer layers and peroxide bleach. It is also possible to spatially separate the peroxide bleaching agent and any bleach activators or bleach catalysts and / or enzymes present in the tablet / shaped article. Such shapes have the advantage that no undesired mutual effects are to be feared in the molded article according to the invention.

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

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

In some embodiments, it has proven to be particularly advantageous to fill the active ingredient compartment (I) in the form of a liquid (generally with a solution and / or melt) or at elevated temperatures to a ready recess in the surrounding active ingredients. generally by drying and / or cooling). A viscosity of more than 1500 mPas, more preferably greater than 2000 mPas, particularly preferably between 2000 and 15000 mPas, very particularly preferably between 2500 and 7000 mPas, and particularly preferably between 3000 and 4000 mPas, has proved to be suitable.

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

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

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japanese wax, esparto wax, cork wax, guaruma wax, rice germ wax, sugar cane wax, ouricury wax or montan wax, animal waxes such as beeswax, shellac wax, shellac wax, shellac wax, shellac wax, shellac wax. spermaceti, lanolin (sheep wool wax) or coccyx fat, mineral waxes such as ceresin or ozokerite (natural wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

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

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

Also within the scope of the present invention, waxes include, for example, so-called wax alcohols. Wax alcohols are high molecular weight water-insoluble fatty alcohols having more than 28 to 40 carbon atoms. Wax alcohols occur, for example, in the form of wax esters of high molecular weight fatty acids (wax acids) as a major component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol) or melisyl alcohol. Optionally, the meltable component may also include sheep wool wax alcohols, which are understood to mean triterpene and steroid alcohols such as lanolin. Also at least partially as the melt component useful in the present invention are fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.

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

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

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

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

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

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

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

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

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

Specific active substances

Particular active ingredients (I) used in the present invention are surfactants. Suitable surfactants are, in principle, all surfactants. Preferred are nonionic surfactants, and in particular weakly foaming nonionic surfactants, but other weakly foaming surfactants are also contemplated. Particularly preferred are alkoxylated alcohols, especially ethoxylated and / or propoxylated alcohols, alkyl polyglycosides and alkyl polyglucamides.

The expert understands thereby Alkoxylated alcohols are generally the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, long-chain alcohols (C 10 to C _8, preferably between C 12 and Cw, such as C n, C 12, C13, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). Generally, from moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, a complex mixture of addition products with different degrees of ethoxylation is formed. Another embodiment consists in using a mixture of alkylene oxides, more preferably a mixture of ethylene oxide and propylene oxide. By means of the final etherification of short-chain alkyl groups, in particular butyl groups, it is also possible to obtain "closed alcohol ethoxylates", which can also be used in the context of the invention, if desired. Highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates are particularly preferred for the purposes of the present invention.

Particularly preferred are alkoxylated hydroxyl-containing alcohols as described in EP 300 305, the teachings of which are expressly incorporated herein. At first, only the cleaning performance of the shaped article was at the center of the assay. However, during the experiments it has been shown that these mixed hydroxyethers exhibit an excellent clear washing effect compared to conventional surfactants. This is particularly advantageous in a mixture with other nonionic surfactants such as Dehypon LS 54, and also in a mixture with Dehydol LS 4, but also a mixture of mixed hydroxyethers and APG. It was unexpected, in addition to the surprising effect of clear washing, that these surfactant mixtures already in the homogeneous mixture decisively reduce stress corrosion in plastics.

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

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

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

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

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

Bleach activators which may be used are compounds which, under peroxohydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acids. Suitable are those having O- and / or Nacyl groups of the indicated number of carbon atoms and / or optionally substituted benzoyl groups. Preferred are multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetyl glycoluril (TAGU) , N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethyl ether , 2,5-diacetoxy-2,5-dihydrofuran, n-methylmorpholinium acetonitrile methyl sulphate (MMA) and enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol, or mixtures thereof ( SORMAN) described in European patent application EP 0 525 239, acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated or optionally alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example Nbenzoyl caprolactam, 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 hydrophilic substituted acyl acetals known from the German patent application DE 196 16 769 as well as the acyllactams described in the German patent application DE 196 16 770 as well as the international patent application WO 95/14075 are also advantageously applicable. It is also possible to use a combination of conventional bleach activators known from German patent application DE 44 43 177. Such bleach activators are included in the conventional quantitative range, preferably in amounts of from 1 wt. % to 10 wt.%, especially from 2 wt. up to 8 wt. relative to the total composition.

In addition to or instead of the above conventional bleach activators, sulfonimines known from European patents EP 0 446 982 and EP 0 453 003 and / or for bleaching of stronger transition metal salts or transition metal complexes may also be included as so-called bleach catalysts. Suitable transition metal compounds include, but are not limited to, manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 195 29 905 and their N-analogous compounds known from German patent application DE 196 20 267, carbonyl complexes of manganese, iron , cobalt, ruthenium or molybdenum known from German patent application DE 195 36 082, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands described in German patent application DE 196 05 688 to ammonium acetate complexes , iron, copper and ruthenium known from German patent application DE 196 20 411, manganese, copper and cobalt complexes described in German patent application DE 44 16 438, cobalt complexes described in European patent application EP 0 272 030, manganese complexes known from European patent application EP 0 693 550, manganese, iron, cob alta and copper known from European patent EP 0 392 592 and / or manganese complexes described in European patent EP 0 443 651 or in European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German Patent Application DE 196 13 103 and International Patent Application WO 95/27775. Preference is given to the use of bleach activators from the group of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), Nacylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate, % in amounts up to 10 wt.%, especially 0.1 wt. % to 8 wt.%, especially from 2 to 8 wt. % and in particular from 2 to 6 wt. relative to the total composition.

Bleach-enhanced transition metal complexes, in particular with central atoms Mn, Fe, Co, Cu, V, Ti and / or Ru, more preferably selected from the group of salts and / or manganese and / or cobalt complexes, particularly preferably (ammonium) -17 complexes cobalt (acetate) cobalt complexes, (carbonyl) cobalt complexes, cobalt or manganese chlorides, manganese sulfate are used in conventional amounts, more preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight. % to 1 wt. % and particularly preferably from 0.01 wt. % to 0.25 wt. relative to the total device. In special cases, more bleach activators may be used.

The dishwashing compositions according to the invention may contain corrosion inhibitors as an active ingredient (I) for the protection of articles or machines to be washed, with silver protection agents being of particular importance in the field of machine dishwashing. Substances known in the art, such as those described in DE 43 25 922, DE 41 28 672 or DE 43 38 724, are usable. and transition metal salts or complexes. Particularly preferred for use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine formulations which can greatly reduce the corrosion of silver surfaces. In the chlorine-free cleaners according to the abovementioned documents, in particular organic redoxactive compounds containing oxygen and nitrogen, such as divalent and trivalent phenols, for example hydroquinone, pyrocatechin, hydroxyhydroquinone, gallic acid, floroglucine, pyrogalol or derivatives of these classes of compounds. Salts and complex inorganic compounds, such as Mn, Ti, Zr, Hf, V, Co and Ce metal salts, are also often used. Preferred are transition metal salts selected from the group of salts and / or complexes of manganese and / or cobalt, particularly preferred are (ammonium) cobalt complexes, (acetate) cobalt complexes, (carbonyl) cobalt complexes, cobalt or manganese chlorides, and manganese sulfate. It is also possible to use zinc compounds to prevent corrosion on washed objects.

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

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

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

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

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

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

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

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

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

The detergent compositions of the present invention may contain from 0 to 5 wt.% To enhance the performance of the detergent composition or to guarantee cleaning performance of the same quality under milder conditions. enzyme relative to the total preparation. The most commonly used enzymes include lipases, amylases, cellulases and

- 19proteases. Preferred proteases are BLAP® 140 from Biozym, Optimase®-M440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal® CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo. Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk are particularly suitable cellulases and lipases. Duramyl® and Termamyl® 60 T, and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades have particular applications as amylases. The use of other enzymes is also possible.

Other active substances

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

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

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

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

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

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

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

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

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

In this connection, it is particularly advantageous according to the invention that the absorption maximum of a 1% solution of the colored space or the colored component during storage under normal household conditions, i.e. between 15 and 30 ° C and between 5 and 55% air humidity, more preferably 15 and 35% air humidity for 30 days,

-21 more preferably 60 days, particularly preferably 90 days, not more than 100 waves, more preferably not more than 50 waves, very particularly preferably not more than 30 waves, particularly preferably not more than 20 waves, and extremely preferably not more than 50 10 wavelengths and most preferably not more than 5 wavelengths.

In particular, as already mentioned, mixed hydroxyethers, as a component of the surfactant group, exhibit an excellent clear washing effect and reduce stress corrosion in plastics. Furthermore, they have the advantage that their wettability is constant over the normal temperature range. The use of the above-mentioned substances as components of clear washing in dishwashing machines has not been described in the prior art. So far only exclusive 'cleaners' or 'clear-cleaners' for machine dishwashing have been published. The combination of these two functions in one composition, as provided by the present invention by incorporating a surfactant component in the space of the molded article having an area of up to 40% of the total volume of the molded article, is novel. Accordingly, a further aspect of the present invention is the use of mixed hydroxyethers and / or mixtures of mixed hydroxyethers and nonionic surfactants as a clear wash component in dishwashing machinery and, secondly, the use of mixed hydroxyethers and / or mixtures of mixed hydroxyethers and nonionic surfactants as a component voltage in machine washing equipment.

Here, it may be advantageous to use not separately mixed hydroxyethers, but to use them in admixture with other surfactants, more preferably nonionic surfactants, and in particular with non-ethoxylated fatty alcohol group surfactants. Uses which are characterized in that the mixed hydroxyether is mixed with fatty alcohol ethoxylates are therefore more preferred. Of course, in a more preferred use of the invention, in addition to ethoxylated fatty alcohols, it is also possible to use propoxylated or ethoxylated and propoxylated fatty alcohols. Such more preferred uses are characterized in that the mixed hydroxyether is mixed with fatty alcohol ethoxy propoxylates.

As described above, the means which simultaneously serve as a machine dishwashing agent and a clear dishwashing means are in

-22 the state of the art is not yet known. The use of mixed hydroxyethers in machine dishwashing detergents has also been unknown. Dishwashing compositions containing mixed hydroxyethers and / or mixtures of mixed hydroxyethers and nonionic surfactants are therefore a further aspect of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

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

When measuring efficacy, the active substance (I) selected was always transferred to the space according to the invention. It was reduced or omitted completely in another area (s) according to the invention prior to the determination.

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

Active substance ra Ra1 VA2 VA3 VA4 VA5 VA6 Ra7 phosphate (sodium tripolyphosphate) 30-60 54.8 56.4 30.5 43 48 48 47 sodium carbonate 5-25 15.9 13.2 21.5 7 20 12 24 disodium silicate 0-40 7.3 7.5 33.7 20 3 14 Polymer (Sokalan CP5) 0-10 2.2 2.2 1 5 sodium metasilicate 0-10 1.8 0 sodium bicarbonate 0-10 1 3 bleach (sodium perborate) 2-20 9.0 9.0 6.7 15 10 12 9 bleach activator (TAED) (Co-pentaammoniacate-CI) 0-5 2.1 2.1 3 2 1 1.5

enzyme (amylase) (Duramyl 60T) 0-5 2.0 2.0 0.7 3 3 3 2.5 enzyme (protease) (Blap 200 S) 0-5 1.8 1.8 1.0 2 2 3 2.5 phosphonate or phosphonic acid 0-5 0.9 0.9 2 1.5 nonionic surfactant (Dehypon LS 54) 0-5 2.0 2.0 2.0 2 4 3 1.5 silver protection (benzotriazole) 0-3 0.3 0.3 0 0.3 0.2 0.5 tableting aid (polyethylene glycol) 0-10 6 paraffin (m.p. 53 ° C) 0-10 2.0 1.0 3 perfume 0-1 0.2 0.2 0.2 1 0.4 1 0.5 coloring 0-4 1.4 1.3 1.4 0.7 0.4 1.5

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

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

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

The test formula (V) used was:

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

(% By weight) may also be used as the frame formulation (R) for the present application: The following test formulation (V) was used:

Active substance rd Rd1 Rd2 Very good 3 Very good 4 trisodium citrate 20-55 44 34 44 44 sodium bicarbonate 5-35 24 9 34 20 carbonate (sodium carbonate) 0-10 7 Polymer (Sokalan CP5) 0-10 6 disodium silicate 0-25 20 bleach (sodium perborate) 0-22 9 16 17 bleach activator (TAED) 0-25 3 1 0 20

enzyme (amylase) (Duramyl 60T) 0,4-5 2.5 3 1 5 enzyme (protease) (Blap 200 S) 0,4-5 2 3 1 5 phosphonate or phosphonic acid 0-5 1.5 2.3 2 nonionic surfactant (Dehypon LS 54) 0-5 2.5 1.7 2 1 silver protection (benzotriazole) 0-3 0.5 0.5 paraffin (m.p. 53 ° C) 0-10 3 1.5 perfume 0-1 0.9 0.5 1 1 coloring 0-4 0.1 1.5 2

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

The test formula (V) used was:

Active substance re Re1 Re2 ve3 Re4 citrate (trisodium citrate) 20-55 32 36 38 24 phosphate (trisodium polyphosphate) 20-55 26 23 24 24 carbonate (sodium carbonate) 1-15 11 10 11 15 Polymer (Sokalan CP5) 0-10 5 1.5 6 silicate (sodium silicate) 0-25 3 6 bleach (sodium perborate) 2-20 16 3 12 9 bleach activator (TAED) 0-5 0.5 5 2 3 enzyme (amylase) (Duramyl 60T) 0-5 5 3 2 enzyme (protease) (Blap 200 S) 0-5 5 0.5 2 phosphonate or phosphonic acid 0-5 2 2 2 tableting aid (polyethylene glycol) 0-10 6 4 5 0.8 nonionic surfactant (Dehypon LS 54) 0-5 2.5 2.8 2 silver protection (benzotriazole) 0-3 0.2 0.2 paraffin (m.p. 53 ° C) 0-10 perfume 0-1 1 1 1 coloring 0-4 0 1 1

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

The test formula (V) used was:

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

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

The test formula (V) used was:

Active substance rg Rg1 Vg2 Rg3 VG4 phosphate (sodium tripolyphosphate) 30-60 55.7 59.6 46.5 47 disodium silicate 5-40 22.3 17.5 39.2 24 Polymer (Sokalan CP5) 0-10 2.2 2.2 5 sodium metasilicate 0-10 1.8 sodium bicarbonate 0-10 bleach (sodium perborate) 2-20 10 10 6.7 10 bleach activator (Co-catalyst) 0-2 1.1 1.1 0.5 enzyme (amylase) (Duramyl 60T) 0-5 2.0 2.0 0.7 2.5

enzyme (protease) (Blap 200 S) 0-5 1.8 1.8 1.0 2.5 phosphonate or phosphonic acid 0-5 0.9 0.9 1.5 nonionic surfactant (Dehypon LS 54) 0-5 2.0 2.0 2.0 1.5 silver protection (benzotriazole) 0-3 0.3 0.3 0 0.5 tableting aid (polyethylene glycol) 0-10 paraffin (m.p. 53 ° C) 0-10 2.0 1.0 3 perfume 0-1 0.2 0.2 0.2 0.5 coloring 0-4 1.4 1.3 1.4 1.5

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

The test formula (V) used was:

Active substance rh Vh1 VH2 VH3 VH4 Rh5 VH6 VH7 phosphate (sodium tripolyphosphate) 30-60 40 40 40 45 45 50 35 sodium metasilicate (5-hydrate) 5-45 45 10 40 10 30 20 35 sodium metasilicate (O-hydrate) 5-40 10 10 8 10 8 5 10 disodium silicate 0-40 0 30 0 15 10 5 0 paraffin oil 0-10 4 5 5 5 6 5 0 bleach (trichloroisocyanic acid) 0,5-10 1 2 2 3 1 5 5 enzyme (amylase) (Duramyl 60T) 0-5 1 2 2 2 enzyme (protease) (Blap 200 S) 0-5 1 2 2 2 nonionic surfactant (Dehypon LS 54) 0-5 2 2 2 2 3 tableting aid (polyethylene glycol) 0-10 1 4 2 4 perfume 0-1 0.3 0.3 1 1 0.5 coloring 0-4 0.7 0.7 1 1 2.5

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

Active substance Ri1 Vi1 Vi2 VI3 sodium carbonate 35-55 43.5 45 55 sodium bicarbonate 15-35 15 25 34 Polymer (Sokalan CP5) 3-10 5 3 0 sodium metasilicate 0-10 3 2 0 bleach (sodium perborate) 5-12 6 10 8 bleach activator (TAED) 0-5 1 2 0 enzyme (amylase) (Duramyl 60T) 0,4-2 1 1 0.5 enzyme (protease) (Blap 200 S) 0,4-2 1 1 0.5 phosphonate or phosphonic acid 0-5 0 2 0 nonionic surfactant (Dehypon LS 54) 0-5 1 2 1 tableting aid (polyethylene glycol) 0-5 3 silver protection (benzotriazole) 0-3 0.5 1 0 paraffin (m.p. 53 ° C) 0-10 0 2 0 perfume 0-1 0 1 0 coloring 0-4 1 1 1

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

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

The manufacture of the shaped articles of the invention utilizes steps known to those skilled in the art in other contexts. A preferred embodiment of the shaped article according to the first claim has a depression in the tablet, the depression containing the active ingredient (I). More preferably, the production is carried out by molding a recess into the shaped article and recessing it.

-29naplní. Pressing can be performed on a Korsch carousel press. In the present case, a Fette tablet press was used. A round tablet form (26 X 36 mm) was chosen and punched 5 mm deep on one side, the base being chosen to fill a volume of 1 ml and the tablet again having a smooth surface.

The liquid mixture of paraffin and the active ingredient (I) (in the present case a surfactant (Dehypon LS 54, mixed hydroxyether, mixtures of both classes of substances)) was then filled and cooled and this cooling can be supported by conventional instrumentation methods.

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

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

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

In one assay, samples analogous to Ra or Va1 were used which contained surfactants as active ingredient (I) once homogeneously distributed in the tablet and once according to claim 1, so that the surfactant components were separated from the other components. The cleaning results were very good.

The results of clear washing were also checked. The effect of using a mixture of a surfactant (mixed hydroxyether) and paraffin in a standard program at 55 ° C was better than the moldings without space (I), homogeneously dispersed component (I) and commercially available cleaners. The results show a positive effect of paraffin. Changing the melting range of paraffin also has an effect on the washing result.

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

In other cases, melt emulsions of various surfactants have been produced in packaging materials that demonstrate positive effects. Here, an embossed shaped product (weight: 24 g) was produced by pressing with a punch having a pin. The composition (in% by weight based on the masterbatch) and thus the deepened molded article is in the following Table 1:

Table 1

Masterbatch composition (wt.%)

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

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

SDE 1 SDE 2 SDE 3 SDE 4 SDE 5 paraffin, mp 57-60 ° C 50 50 50 50 50 emulsifier * - - 5 5 5 Dehypon® LS 54 ** 50 - 45 - - Dehypon® LT 104 *** - 50 - 45 - Poly-Tergent® SLF 18B45 - - - - 45

-31 * poly (12-hydroxystearic acid) polyglycerol, Dehymuls ~ KE 3360 (Gronau) ** C ₂ -i4 fatty alcohol containing 5 EO and 4 EO (Henkel) *** fatty alcohol polyglycol ether, modified (Henkel) * *** fatty alcohol alkoxylate (Olin Chemicals)

The melt emulsions were filled into the shaped articles as described above and allowed to cool. Here the molded articles had a weight of 24 g before filling and were always filled with 1.3 g of the melt emulsion. The cleaning performance (clear wash effect) of molded products E1 to E5 filled with melt emulsions SDE 1 to SDE 5 was tested on various substrates (plates, cups, knives, plastic plates). To do this, the soiled items were cleaned in a household dishwasher whose rinse aid container was emptied:

The effect of the clear detergent was visually inspected and evaluated by experts, with a scale of 0 to 8 indicating "0" stains from the water and no difference from washing without rinse aid and "8" meant absolutely clean.

The clear wash effect was measured under the wash conditions of 55 ° C / 16 ° d water hardness in the main wash program (i.e., "hard conditions"). Miele G 590 with a universal program was used as a dishwasher. The following table shows the results obtained for the clear washing of E1 to E5 compared to the unfilled molded product V:

IN E1 E2 E3 E4 E5 plates 4.7 6.8 6.7 6.7 6.6 6.7 cups 3.8 4.9 4.6 4.8 4.5 5.4 knives 4.0 5.2 4.3 5.1 4.2 5.3 plastic plates 3.9 4.3 4.1 4.2 4.0 5.3

The results show that the molded articles E1 to E5 according to the invention outweigh the comparative molded article V in obtaining clear washing effects.

Claims (24)

PATENT CLAIMS 1. A molded article containing activating agents, alkalinity sources, bleaching agents and enzymes, characterized in that in a space not exceeding 40% by volume of the composition, contains more than 80 wt. active ingredient (I) with a surfactant component. Shaped product according to claim 1, characterized in that the space is between 1 and 30% by volume, preferably between 2 and 25% by volume, most preferably between 3 and 20% by volume. The molded article comprises more than 90 wt.%, more preferably more than 95 wt. and most preferably the total amount of active ingredient (I). Shaped product according to claim 1, characterized in that the active substance (I) is a mixture of a surfactant and another substance selected from the group consisting of a bleach activator and / or a bleaching agent from the group of chlorine and / or oxygen bleaching agents and / or a silver preservative and / or an enzyme and / or a soil release compound and / or a solubility control component and / or other active ingredients. A shaped article according to any one of the preceding claims, characterized in that the at least one oxygen-based bleaching agent is selected from the group consisting of alkali perborates, alkali percarbonates, organic peracids and hydrogen peroxide. Molded article according to any one of the preceding claims, characterized in that the active ingredient (I) is composed of at least one surfactant and at least one fusible component for controlling solubility selected from the group of surfactants, paraffins, micro-waxes and / or high molecular weight polyethylene glycols and / or disintegrator. Molded article according to any one of the preceding claims, characterized in that a bleach activator is present, preferably from the group of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSi), acylated especially n-nonanoyl or isononanoyloxybenzenesulfonate (optionally iso-NOBS), M MA and / or from the group of salts and / or manganese and / or cobalt complexes, particularly preferably (ammonium) cobalt complexes, (acetate) cobalt complexes, (carbonyl) cobalt complexes, cobalt or manganese chlorides, manganese sulphate preferably in amounts of from 1 wt% to 10 wt%, in particular from 2 wt%. % to 8 wt. relative to the total device. Molded article according to any one of the preceding claims, characterized in that it contains one or more activating agents from the group of gluconates, low molecular weight polycarboxylic acids and their salts, homopolymeric and copolymeric polycarboxylic acids and their salts, carbonates, phosphates and silicates, more preferably citrate. pentasodium trisodium and / or tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate activating agents of the class of silicates and / or metasilicates. Molded article according to any one of the preceding claims, characterized in that it contains as a builder system a mixture of tripolyphosphate and / or sodium carbonate and / or sodium disilicate. Molded article according to any one of the preceding claims, characterized in that the surfactants are selected from the group of nonionic surfactants, more preferably low foaming nonionic surfactants, very particularly preferably from alkoxylated and / or propoxylated fatty alcohols, alkylpolyglycosides, alkylpolyglucamides and / or mixtures of the preceding surfactants. , more preferably from the group of mixed hydroxyethers and mixtures of mixed hydroxyethers and other nonionic surfactants. Molding according to any one of the preceding claims, characterized in that at least one silver protecting agent selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, in particular benzotriazole and / or alkylaminotria, is additionally present. . Molded article according to claim 10, characterized in that the transition metal salts are selected from the group of salts and / or complexes of manganese and / or cobalt, particularly preferably (ammonium) cobalt complexes, (acetate) cobalt complexes, (carbonyl) - cobalt complexes, cobalt or manganese chlorides and manganese sulphate. Molding according to any one of the preceding claims, characterized in that the component and / or the components for controlling solubility are selected from the group of paraffins, micro-waxes and high molecular weight polyethylene glycols. Molded article according to any one of claims 1 to 12, characterized in that a component and / or a solubility control component selected from the group of organic acids, such as citric acid or citric acid / bicarbonate mixture and / or cellulose and cellulose derivatives. Molding according to any one of the preceding claims, characterized in that the bleaching component (s), in particular the chlorine component (s), are not packaged in one phase with the perfume component. A shaped article according to any one of the preceding claims, characterized in that the silver protection component is not packaged together with any of the bleaching components. Molded article according to any one of the preceding claims, characterized in that at least one of the components for controlling solubility is packaged together with a bleach activator. A shaped body according to any one of the preceding claims, characterized in that at least one of the components for controlling solubility is packaged together with enzymes. A shaped article according to any one of the preceding claims, characterized in that at least one of the components for controlling solubility is packaged together with a bleaching agent. A shaped body according to any one of the preceding claims, characterized in that at least one of the components for controlling solubility is packaged together with the silver protecting component. Use of mixed hydroxyethers and / or mixtures of mixed hydroxyethers and nonionic surfactants as a component of clear washing in machine dishwashing compositions. Use of mixed hydroxyethers and / or mixtures of mixed hydroxyethers and nonionic surfactants as a component for preventing stress corrosion in machine dishwashing compositions. Use according to claim 20 or 21, wherein the mixed hydroxyether is in admixture with fatty alcohol ethoxylates. The use according to claims 20 to 22, wherein the mixed hydroxyether is in admixture with fatty alcohol ethoxy propoxylates. A dishwashing composition, characterized in that it comprises a mixed hydroxyether and / or a mixture of mixed hydroxy ethers and nonionic surfactants.