EP0842257B1 - Dish washer product in tablet form - Google Patents

Abstract

The invention relates to a dishwasher detergent in the form of a multi-layer tablet comprising a bleach, a bleach activator, a silver/copper corrosion inhibitor and also other customary constituents, where the silver/copper corrosion inhibitor is not present together with the bleach and the bleach activator in one layer.

Description

The present invention relates to a Dishwasher detergent in the form of a tablet containing a bleach and a bleach activator and other common ingredients.

Conventional detergents for machine cleaning of Dishes are generally powdered, granular or liquid products. Tablet-shaped Detergent compositions have also been around for some Years known. In principle, have tablet-shaped products some advantages over powder and liquid Products: You do not need precise dosing and are therefore easier to handle and in the dishwasher they are more compact and therefore require less Packaging material and storage space and they are in the household safer to use because spillage aggressive substances is not possible.

However, it has been found that Tablet detergent compositions deteriorated cleaning effect compared to those in Can have powder form. This can be attributed to this be that the individual in compressed tablets Components are much closer together than in powders, so that negative interactions, the individual Exercise components on each other, occur more can. This can lead to partial inactivation individual components come. The applicant now has found that such a problem also occurs in the combined use of bleaching agents and bleach activators with means that tarnish non-ferrous metals prevent, especially with silver / copper anti-corrosion agents.

Another problem with Dishwasher detergent occurs in tablet form and the washing performance deteriorates is that such Dishwasher detergents are less effective than comparable powder since the tablets dissolve more slowly and therefore in the wash liquor only later than in the Use of powders are available. This problem occurs particularly in dishwashing detergents, which contain a bleaching agent, since when such Tablet means one necessary for bleaching Bleach concentration is relatively late during the Rinsing process is reached. In EP-A 504 091 Solution to this problem suggested a certain one Combination of alkali carbonate, polycarboxylate, one polyfunctional carboxylic acid, sodium silicate, one use nonionic surfactant and the bleach, so the bleaching effect is obtained with compressed tablets remains.

EP-A 634 478 discloses machine dishwashing detergents nitrogen-containing corrosion inhibitors and one oxygen-releasing bleach. According to the explanations In this document, the dishwasher detergents can be found in any shape, and it will also be on the edge Tablets mentioned, obviously the difficulties the in the formulation of corrosion inhibitors Bleaching agents or bleach activators cannot occur were recognized.

EP-A 481 547 discloses that during storage a Dishwasher detergent and in the aqueous Cleaning solution in a dishwasher enzymes in Be deactivated in the presence of a chlorine bleach. For EP-A 481 547 discloses a solution to this problem Dishwasher detergent with enzymes and chlorine bleach in the form of a complex structure, at least three layers Tablet that has an inner layer, a barrier layer and a contains outer layer. The enzymes and the chlorine bleach are separated in different layers of the tablet. This complex structure of detergent tablets is said to make sure that none during storage Interface between the one containing the chlorine bleach Layer and the layer containing the enzyme and for other the two layers not at the same time but are dissolved one after the other and therefore the chlorine bleach and the enzymes are not simultaneously in the rinse water Dishwasher available.

EP-A 481 793 discloses detergent compositions in tablet form, the sodium percarbonate as a bleach included and used in textile washing machines should. In order to be able to obtain a storage-stable tablet, the In addition to sodium percarbonate, other ingredients that are associated with the Bleach can interact, contains, will suggested the percarbonate in the tablet from the others Separate components, for example in two layers. The tablets produced in this way are also said to be increased Have a dissolving speed in the wash liquor.

EP-A 481 792 describes a product in tablet form Treatment of fabrics in washing machines disclosed that Improve the bleaching effect of a combination of one Contains persalt and a bleach activator, the Bleach activator a certain rate constant for which must have perhydrolysis.

DE-OS 25 27 534 discloses a multilayer Cleaning tablet for artificial dentures, the first Layer contains an enzyme and is in front of the second, active Dissolves layer containing oxygen. This can Enzyme initially act without being released from the active Oxygen to be deactivated.

EP-A 541 475 and WO-A 95/01416 disclose Detergents that can be in the form of a tablet and the bleach, bleach activator and silver / copper corrosion inhibitor can contain. The possibility of this Separating components is not disclosed.

It is an object of the present invention to provide a Dishwashing detergent in the form of a tablet for To provide that in addition to a bleach and a Bleach activator and other common ingredients Contains means that the tarnishing of non-ferrous metals on the prevents dishes to be cleaned, especially a silver / copper anti-corrosion agent, the agent, in particular the silver / copper anti-corrosion agent, the effectiveness of the Tablet not impaired, but at least one good, preferably even better washing performance as with one comparable powder is achieved.

Another object of the invention is to provide a Dishwashing detergent in the form of a tablet for To provide that in addition to a bleach and a Bleach activator and other common ingredients Contains means that the tarnishing of non-ferrous metals on the prevents dishes to be cleaned, especially a silver / copper anti-corrosion agent, the remedy, although it is in Tablet form is present and the individual components of the Wash liquor only at a later stage of the Flushing are available, at least as well good, preferably better washing performance shows how that Powder form.

It has now surprisingly been found that such tablets, the consist of at least two layers, the mean that Prevent or reduce the tarnishing of non-ferrous metals should, especially the silver / copper anti-corrosion agent, not together in one layer with the bleach and the activator is included, an unabated or even improved cleaning effect compared to powders of the same type Have composition and this, although the tablet only dissolves in the course of the rinsing process and the components of the Therefore only in a later stage of the rinsing process be available.

These effects do not only occur Dishwashing detergents after a certain Storage time, but surprisingly also at Dishwashing detergents immediately after production, so that the effects are independent of interactions in the Means that can take place during storage occur.

The present invention thus relates to Dishwasher detergent in the form of a tablet containing a bleach, a bleach activator and a Means that prevent tarnishing of non-ferrous metals or should reduce, in particular a silver / copper corrosion protection agent, as well as other common ones Ingredients, characterized in that the tablet consists of at least two layers, the mean that the Prevent or reduce tarnishing of non-ferrous metals, especially the silver / copper anti-corrosion agent, not together in one layer together with the bleach and the bleach activator is included.

The tablet according to the invention dissolves in the liquor in the Dishwasher preferably not faster than three Minutes completely.

Under "completely dissolve" is understood here that the Tablets have fallen apart so far that they are in moving water emerge at 40 ° C through a basket with 4 mm openings can.

Dishwashing detergents according to the invention preferably contain chlorine-free, active bleaching agents Oxygen-releasing bleaches such as inorganic Perhydrates or organic peracids and their salts.

Examples of inorganic perhydrates are perborates, Percarbonates and persulfates such as peroxymonopersulfates. The inorganic perhydrates are usually alkali metal salts, such as lithium, sodium, potassium or rubidium salts, especially the sodium salts. The inorganic perhydrates can in the detergent as crystalline solids without one protection. For certain perhydrates it is however advantageous to use them as granular compositions use with a coating that the gives granular products better storage stability.

The preferred perborate is sodium perborate, which can be present as a monohydrate with the formula NaBO ₂ H ₂ O ₂ or as a tetrahydrate with the formula NaBO ₂ H ₂ O ₂ .3H ₂ O.

The preferred percarbonate is sodium percarbonate with the formula 2Na ₂ CO ₃ 3H ₂ O ₂ . The percarbonate is preferably used in a coated form to increase its stability.

Organic peracids all conventionally include Bleach used organic peracids, including, for example, perbenzoic acid and Peroxycarboxylic acids such as mono- or diperoxyphthalic acid, 2-octyldiperoxysuccinic acid, Diperoxydodecanedicarboxylic acid, Diperoxyazelaic acid and imidoperoxycarboxylic acid as well where appropriate, their salts.

Chlorine-containing bleaches such as Sodium dichloroisocyanurate or sodium trichloroisocyanurate in be included in the detergent according to the invention.

The bleach is usually 1 to 40 wt .-%, preferably from 2 to 30 wt .-% and am most preferred from 5 to 20% by weight of the total weight of the Tablet in the detergent.

The dishwashing detergent according to the invention contains one or more bleach activators. These will preferably in detergents for dishwashing Temperatures used in the range below 60 ° C to a to achieve sufficient bleaching effect. Particularly suitable for example, N- and O-acyl compounds such as acylated Amines, acylated glycolurils or acylated Sugar compounds. N, N, N ', N'-tetraacetylethylene diamine are preferred (TAED), pentaacetylglucose (PAG) and Tetraacetylglycoluril (TAGU). But are also suitable catalytically active metal complexes and preferred Transition metal complexes as bleach activators. The most TAED is preferred.

Further suitable bleach activators are described in WO 95/01416 hereby expressly refers to the content thereof is taken.

The bleach activator can be used in the detergent according to the invention in an amount in the range of 0.1 to 20% by weight and preferred from 1 to 10% by weight of the total weight of the tablet.

The dishwashing detergent according to the invention contains still a means of tarnishing non-ferrous metals, Prevent or reduce especially silver and copper should, especially silver / copper anti-corrosion agents. Preferred silver / copper corrosion inhibitors are Benzotriazole or bis-benzotriazoles and their substituted Derivatives.

Other suitable agents are organic and / or inorganic redox-active substances and paraffin oil.

Benzotriazole derivatives are compounds in which the available substitution sites of the aromatic ring are partially or completely substituted. Linear or branched chain C _1-20 alkyl groups as well as hydroxy, thio, phenyl or halogen such as fluorine, chlorine, bromine and iodine are suitable as substituents. Preferred substituted benzotriazole is tolyltriazole.

Suitable bis-benzotriazoles are those in which the benzotriazole groups are each connected in the 6-position by a group X, in which X is a bond, a straight-chain alkylene group which is optionally substituted by one or more C _1-4 alkyl groups and preferably has 1-6 carbon atoms , a cycloalkyl radical having at least 5 carbon atoms, a carbonyl group, a sulfuryl group, an oxygen or a sulfur atom. The aromatic rings of the bis-benzotriazole can be substituted as defined above for the benzotriazole.

Suitable organic redox-active substances are, for example, ascorbic acid, indole, methionine, an N-mono- (C ₁ -C ₄ alkyl) glycine, an N, N-di (C ₁ -C ₄ alkyl) glycine, 2- phenylglycine or a coupler and / or developer compound chosen from the group of diaminopyridines, aminohydroxypyridines, dihydroxypyridines, heterocyclic hydrazones, aminohydroxypyrimidines, dihydroxypyrimidines, tetraaminopyrimidines, triaminohydroxypyrimidines, Diaminodihydroxypyrimidine, Dihydroxynaphtaline, naphthols, pyrazolones, hydroxyquinolines, aminoquinolines, primary aromatic amines, which in ortho, meta or para position have a further free or with C ₁ -C ₄ alkyl or C ₂ -C ₄ hydroxyalkyl groups substituted hydroxy or amino groups and the di- or trihydroxybenzenes.

Suitable inorganic redox-active substances are for example, metal salts and / or metal complexes selected from the group of manganese, titanium, zirconium, hafnium, Vanadium, cobalt and cerium salts and / or complexes, wherein the Metals in one of the oxidation states II, III, IV, V or VI available.

Metal salts and / or metal complexes selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1 are particularly suitable -diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ .

Organic and inorganic redox-active substances, which as Silver / copper anti-corrosion agents are suitable also mentioned in WO 94/26860 and WO 94/26859, on the Content hereby referred.

Suitable paraffin oil are predominantly branched aliphatic hydrocarbons with a number of carbon atoms in the range from 20 to 50. The paraffin oil is preferably selected from predominantly branched chain C _25-45 species with a ratio of cyclic to noncyclic hydrocarbons of 1:10 to 2: 1 , preferably from 1: 5 to 1: 1.

The agent that prevents tarnishing of non-ferrous metals or should reduce, especially the silver / copper corrosion protection agent, lies in that Dishwasher detergent of the present invention preferably with 0.01 to 5% by weight, particularly preferably with 0.1 up to 2% by weight of the total weight of the tablet.

The dishwashing detergent according to the invention can still contain other common ingredients. For this include builders, masking agents, surfactants Agents, enzymes, foam control agents, fragrances, dyes and other auxiliary substances.

Suitable builders are, for example, homo- and copolymeric polycarboxylic acids and their partial or fully neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts, carbonates, Bicarbonates, borates, phosphates, silicates, aluminosilicates and mixtures of such substances.

Preferred salts of the above compounds are Ammonium and / or alkali salts, i.e. the lithium, sodium, Potassium and rubidium salts and particularly preferably that Sodium salt used.

Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, these contain at least two carboxy groups, each through preferably no more than two carbon atoms from each other are separated.

Polycarboxylates containing two carboxy groups include for example water-soluble salts of succinic acid, Malonic acid, (ethylenedioxy) diacetic acid, maleic acid, Diglycolic acid, tartaric acid, tartronic acid and fumaric acid. Polycarboxylates containing three carboxy groups include for example, water-soluble citrates. Suitable accordingly citric acid, for example, as the hydroxycarboxylic acid.

The homopolymer of is also suitable as the polycarboxylic acid Acrylic acid.

In addition to borates such as sodium borate, borate builders can be used such builders are also used, the borate-forming Contain materials that include borates Detergent storage conditions or rinsing conditions release.

Suitable phosphates are polyphosphates such as tripolyphosphate, Pyrophosphate, orthophosphate and the polymeric metaphosphate. For example, alkali tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate and also called sodium polymetaphosphate, in which the Degree of polymerization preferably ranges from 5 to 21.

Suitable silicates are sodium silicates such as sodium disilicate, Sodium metasilicate and crystalline layered silicates. Farther sodium aluminosilicates (zeolites) are suitable.

Further suitable builders are described in WO 95/01416 hereby expressly refers to the content thereof is taken.

The dishwashing detergent according to the invention can from 40 to 90 wt .-%, preferably from 60 to 80 wt .-% of the Total tablet weight of builders included. Both individual builders and Mixtures of various builders mentioned above be used. For example, mixtures of Carbonates and silicates.

Suitable masking agents for complexing Heavy metal ions that are used according to the invention can be organic phosphonates such as Aminoalkylene poly (alkylene phosphonate), alkali-ethane-1-hydroxydiphosphonate and nitrilotrimethylene phosphonates.

Preferred phosphonates are diethylene triamine penta (methylene phosphonate), Hexamethylene diamine tetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate. Farther aminopolycarboxylates such as are suitable Nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) as well as polyaspartates.

According to the invention, the masking agent can contain a proportion from 0.01 to 10% by weight, preferably from 0.1 to 2% by weight on Total weight of the tablet should be present.

For example, nonionic surfactants are suitable as surfactants. These include, for example, water-soluble ethoxylated C _6-16 fatty alcohols and C _6-16 mixed ethoxylated / propoxylated fatty alcohols and mixtures thereof, and also alkyl polyglucosides.

Another class of nonionic surfactants includes polyhydroxy fatty acid amides.

Further suitable surface-active agents are described in WO 95/01416, the content of which is hereby expressly disclosed Reference is made.

According to the invention, the surface-active agent can be treated with a Proportion of 0.1 to 10 wt .-%, preferably from 1 to 5 wt .-% am Total weight of the tablet should be present.

The dishwashing detergent according to the invention can further one or more conventionally used herein Enzymes selected from, for example, proteases, amylases, Contain lipases and esterases.

The enzymes can be in the detergent with a content of 0.1 to 10 wt .-%, preferably 1 to 5 wt .-% of the total weight of the Detergent must be present.

The dishwashing detergent according to the invention can further contain one or more foam control agents. All those used in this area are suitable for this Foam control agents such as silicones and Paraffin oils.

The foam control agents are in the invention Dishwasher detergent preferably with less than 5 Weight percent of the total weight of the detergent included.

Furthermore, the dishwashing detergent according to the invention can other usual additives such as Contain fragrances, dyes and / or other auxiliaries. For example, as auxiliaries that are used to manufacture the Tablets facilitate different polymers like Polyvinyl pyrrolidone, polyvinyl polypyrrolidone or Polyethylene glycol (preferably with a molecular weight of 100-10,000) or glycerin can be used.

A preferred dishwashing detergent according to the invention consists of two layers, the first layer a) as a bleaching agent a perborate, b) as Builders sodium tripolyphosphate, a disilicate and a Carbonate, c) a nonionic surfactant, d) as silver / copper corrosion inhibitor benzotriazole as well optionally contains other auxiliaries and the second Layer a) as bleach activator N, N, N ', N'-tetraacetylethylenediamine, b) sodium tripolyphosphate as builders, a homopolymeric acrylic acid polymer and a Carbonate, c) a phosphonate as a masking agent, d) a nonionic surfactant, e) one or more Contains enzymes and optionally other auxiliaries.

Another preferred dishwashing detergent according to the invention consists of two layers, the first layer a) as a bleaching agent a perborate, b) as Builders a citrate, a bicarbonate and a carbonate, c) a nonionic surfactant, d) as a silver / copper corrosion inhibitor Benzotriazole as well optionally contains other auxiliaries and the second Layer a) as bleach activator N, N, N ', N'-tetraacetylethylenediamine, b) as builders citrate, a Bicarbonate, a carbonate, a homopolymeric acrylic acid polymer and citric acid, c) a phosphonate as masking agent, d) a nonionic surfactant, e) one or several enzymes and possibly other auxiliary substances contains.

The tablets of the present invention can be made by any conventional method known in the art. For example, the constituents of the individual layers are premixed separately and then pressed together in layers to obtain a tablet. The hardness of the tablet and the time it takes for the tablet to dissolve completely depend, among other things, on the pressure used during the pressing process. The lower the pressure during the pressing process, the more crumbly the tablet obtained and the faster it dissolves in the wash liquor. A higher pressure leads to firmer tablets, which dissolve correspondingly more slowly. For example, pressures of 0.01 to 70 kN / cm ² are suitable for the pressing process.

The pressing process can also be defined by the force the tablet thus obtained break. Such measurements of the hardness of the tablet can for example with an Erickson 464H endurance test machine be performed. Those of the invention preferably have Tablets a hardness of 90-130 N.

The size of the tablet according to the invention depends on the Desired amount of dishwashing detergent, which the Tablet should contain. The tablet can be, for example, 15-25 weigh g. The tablet preferably contains the Dishwasher detergent amount that for one Dishwashing process is needed. The tablet can also consist of larger units for dosing for example at a predetermined breaking point into smaller ones Parts in dose form can be broken.

The tablet can be of any suitable shape, especially with constant thickness, e.g. round or rectangular, exhibit.

The following examples are intended to further illustrate the present invention explain. Percentages are given in percent by weight.

example 1

Two-layer tablets of the following composition (Table 1) were made using a high speed rotary press Made on a production scale. The Tablets weighed a total of 18 g, with 12.6 g in the first Layer and 5.4 g were in the second layer. A powdered composition with the same amounts of Ingredients like the total amount in the two-layer tablet was also made (Table 1). One and only The difference between the two preparations was that Product form. The tablet was pressed so that the force that needed to break the tablet, approximately 110 N scam. This measurement was made using an Erickson 464H hardness test machine performed.

The dissolution rate of the tablets was also determined. The determination was made by measuring the time it took for the tablet to disintegrate to the point where it could exit through 4 mm openings in a basket submerged in moving water at 40 ° C. This result is also shown in Table 1. Components 1st shift% 2 layer % whole tablet% Powder% Perborate 16.00 11.20 11.20 TAED 6.83 2.05 2.05 NTPP 48.00 50.87 48.86 48.86 Disilicate 5.00 3.50 3.50 Carbonate 18.64 25.51 20.70 20.70 Phosphonate 2.72 0.82 0.82 polymer 2.72 0.82 0.82 Nonionic surfactant 4.50 2.07 3.77 3.77 Protease 3.37 1.01 1.01 Amylase 1.33 0.40 0.40 BTA 0.36 0.25 0.25 PEG 6.00 4.08 5.42 5.42 Glycerin 1.50 0.50 1.20 1.20 total 100 100 100 100 resolution approx. 10 min 0 min

The effect of both the two-layer tablet and the Powder of the same composition was then according to DIN 44990 certainly. This method describes the testing of Dishwashing detergents via a visual determination of the effect on a scale of 1 to 5 (with 5 being perfectly clean Is accepted). A dishwashing machine from Bosch was used with the normal 65 ° C wash program. The water hardness was 18 ° d. Five washes were made for each product carried out, in any case the product automatically dosed by the machine's own detergent dispenser has been.

The results for the essential enzyme-relevant pollution, milk, are shown in Table 2. pollution Two-layer tablet powder milk 3.22 3.08

Example 2

Two-layer tablets were produced using a high-speed rotary press on a production scale. The tablets weighed 20 g, the first layer contained 14 g and the second layer 6 g (Table 3). The tablets were pressed sufficiently to obtain a hardness of 100 N (same hardness test machine as in Example 1). Again, a powdered composition of the same formulation was also made (Table 3). The dissolution time of the two-layer tablets is given in Table 3. Components 1st shift% 2 layer % whole tablet% Powder% Perborate 14.3 10.01 10.01 TAED 25.00 7.50 7.50 Citrate 50.01 26.37 42.92 42.92 Bicarbonate 24.57 17.20 22.36 22.36 Carbonate 7.21 4.78 6.48 6.48 Phosphonate 1.66 0.50 0.50 polymer 1.66 0.50 0.50 Citric acid 10.00 3.00 3.00 Nonionic surfactant 3.00 1.00 2.40 2.40 Protease 9.00 2.70 2.70 Amylase 3.30 0.99 0.99 BTA 0.36 0.25 0.25 Glycerin 0.50 0.35 0.35 Perfume 0.05 0.04 0.04 Fragrance 0.03 0.01 0.01 total 100 100 100 100 resolution approx. 8 min 0 min

The effect of both the two-layer tablet and the Powder of the same composition was then according to DIN 44990 certainly. It was a dishwashing machine from Bosch the normal 65 ° C washing program. The water hardness was 18 ° d.

The results for the essential enzyme-relevant contamination, milk, are shown in Table 4. pollution Two-layer tablet powder milk 3.20 2.88

Comparative Example 3

In this example, single-layer tablets were made according to a composition already on the market. The tablets were pressed so that the strength of the tablet was approximately 125 N. The dissolution time was also measured, the results are shown in Table 5. A powdery composition of the same formulation was also made. The composition is given in Table 5. Components Single-layer tablet% Powder% Carbonate 16.60 16.60 Percarbonate 21.90 21.90 NTPP 45.70 45.70 Disilicate 5.90 5.90 Phosphonate 2.00 2.00 PEG 1.00 1.00 Protease 1.0 1.0 Amylase 0.4 0.4 Nonionic surfactant 4.25 4.25 BTA 0.25 0.25 Glycerin 1.00 1.00 total 100 100 resolution approx. 13 min 0 min *

The effect of both the tablet and the powder was again determined according to DIN 44990. As before, one Dishwasher from Bosch used. Again it was normal 65 ° C wash program used and the water had one Hardness of 18 ° d.

The results for the essential enzyme-relevant contamination, milk, are shown in Table 6. pollution Single-layer tablet powder milk 3.31 3.88

These examples and comparative examples clearly show that an inventive dishwashing detergent, that is constructed as a simple two-layer tablet, one achieves better washing performance than a comparable powder, although the individual components of the invention Completely after about 8 to 13 minutes for the Flushing performance is available while at a comparable powder all ingredients are immediately available stand.

Claims (8)

1. A dishwasher detergent in the form of a tablet comprising a bleach, a bleach activator and an agent for preventing or minimizing the tarnish of non-iron metals, and other customary constituents, characterized in that the tablet consists of at least two layers, wherein the agent for preventing or minimizing the tarnish of non-iron metals is not present together with the bleach and the bleach activator in one layer.
2. A dishwasher detergent as claimed in claim 1, characterized in that the total tablet dissolves completely in the liquor of the dishwasher not faster than in three minutes.
3. A dishwasher detergent as claimed in either of the preceding claims, characterized in that the agent for preventing or minimizing the tarnish of non-iron metals comprises one or more compounds selected from the group consisting of benzotriazole and bisbenzotriazoles, where the available substitution positions of the aromatic ring(s) can be partially or fully substituted,- organic and/or inorganic redox-active substances and paraffin oil.
4. A dishwasher detergent as claimed in any of the preceding claims, characterized in that the bleach comprises one or more compounds selected from the group consisting of perborates, percarbonates, peroxomonopersulphates and organic peracids and also their salts.
5. A dishwasher detergent as claimed in any of the preceding claims, characterized in that the bleach activator comprises one or more compounds selected from the group consisting of N,N,N',N'-tetraacetylethylenediamine (TAED), pentaacetylglucose (PAG), tetraacetylglycoluril (TAGU) and catalytically active metal complexes.
6. A dishwasher detergent as claimed in any of the preceding claims, characterized in that it contains additionally one or more constituents selected from the group consisting of builders, sequestering agents, chlorine bleaches, surface-active agents, enzymes, foam inhibitors, fragrances, dyes and other auxiliaries.
7. A dishwasher detergent as claimed in any of the preceding claims, consisting of two layers, where the first layer comprises a) a perborate as bleach, b) sodium tripolyphosphate, a disilicate and a carbonate as builders, c) a nonionic surface-active agent, d) a benzotriazole as agent preventing or minimizing the tarnish of non-iron metals and optionally further auxiliaries and the second layer comprises a) N,N,N',N'-tetraacetylethylenediamine as bleach activator, b) sodium tripolyphosphate, a homopolymeric acrylic acid polymer and a carbonate as builders, c) a phosphonate as sequestering agent, d) a nonionic surface-active agent, e) one or more enzymes and optionally further auxiliaries.
8. A dishwasher detergent as claimed in any of claims 1 to 7, consisting of two layers, where the first layer comprises a) a perborate as bleach, b) a citrate, a bicarbonate and a carbonate as builders, c) a nonionic surface-active agent, d) benzotriazole as agent for preventing or minimizing the tarnish of non-iron metals and optionally further auxiliaries and the second layer comprises a) N,N,N',N'-tetraacetylethylenediamine as bleach activator, b) citrate, a bicarbonate, a carbonate, a homopolymeric acrylic acid polymer and citric acid as builders, c) a phosphonate as sequestering agent, d) a nonionic surface-active agent, e) one or more enzymes and optionally further auxiliaries.