DE10015289A1 - Particulate machine dishwashing detergent with rinse aid effect - Google Patents

Abstract

The invention relates to particle-shaped dishwashing machine detergents whose content of non-ionic surfactants is equal to 5 to 25 wt. % with regard to the entire detergent. Said detergents can be used in dishwashing methods in which no additional clear rinsing agent must be added. These methods for cleaning dishes in a domestic dishwashing machine while using particle-shaped dishwashing machine detergents involve the following steps: bringing the dirty item to be washed into contact with an aqueous cleaning bath consisting of water and of the particle-shaped dishwashing machine detergent, whereby the particle-shaped dishwashing machine detergent contains 5 to 25 wt. % of non-ionic surfactant(s); pumping out the cleaning bath, and; subjecting the item to be washed to a clear rinsing cycle.

Description

The present invention is in the field of automatic dishwashing detergents household dishwashers. It particularly concerns particulate ma Fast dishwashing detergents (MGSM) that produce a rinse aid effect.

The mechanical cleaning of dishes in household dishwashers includes übli a pre-rinse, a main rinse and a rinse cycle, which are from Zwi rinse cycles are interrupted. Most machines have the pre-rinse cycle can be switched on for heavily soiled dishes, but is only used in exceptional cases by the Ver user selected, so that in most machines a main wash, an intermediate rinse clean water and a rinse cycle. The temperature of the The main wash cycle varies depending on the machine type and program level selection 40 and 65 ° C. In the rinse cycle, a dosing tank in the machine turns into rinse aid agents added, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely used in the prior art wrote. Your job is primarily to keep limescale and deposits on the ge to prevent cleaned dishes. In addition to water and low-foaming non-ionic surfactants these rinse aids often also contain hydrotropes, pH adjusting agents such as citric acid or scale-inhibiting polymers.

The storage tank in the dishwasher must be clear at regular intervals dishwasher can be filled, with one filling for 10 to 50 rinse cycles depending on the machine type sufficient. If the refilling of the tank is forgotten, glasses in particular  unsightly due to limescale and deposits. There are therefore some in the prior art Proposed solutions, a rinse aid in the detergent for machine wash to integrate dishwashing. These proposed solutions are based on the offer form of the kom compact molded body bound.

For example, European patent application EP-A-0 851 024 (Unilever) describes two layers ge detergent tablets, the first layer of peroxy bleach, builder and enzyme contains while the second layer of acidifying agent and a continuous medium with a melting point between 55 and 70 ° C and scale inhibitors. By the high-melting continuous medium should the acid (s) and deposit inhibitor (s) are released with a delay and produce a rinse aid effect. Powdered machi Normal dishwashing detergents or surfactant-containing rinse aid systems are not described in this document mentioned.

The older German patent application DE 198 51 426.3 (Henkel KGaA) describes a Ver drive to the production of multi-phase detergent tablets, in which a particulate premix is pressed to form bodies which have a trough sen, which later with a separately prepared melt suspension or emulsion from a Envelope and one or more active dispersed or suspended in it substance (s) is filled. The teaching of this writing is also based on the "tablet" bound. Powdered cleaners containing a "second phase", which by kon controlled release of ingredients achieve certain effects, are not open beard.

Dishwashing systems for commercial dishwashers without the deliberate addition of rinse aid will result in a rinse aid international application WO 98/32823 (Ecolab). The one described there Cleaning method includes the use of a high surfactant, through which Use sufficient nonionic surfactant held on the dishes and the baskets of the machine in order to get into the rinse aid and there to provide a rinse aid effect. The System is characterized by the disadvantage of extremely high non-ionic surfactant contents (<30% by weight) and only works in commercial machines without an intermediate rinse cycle.  

Automatic dishwashing detergents containing rinse aid particles are used in the older ones German patent applications DE 199 14 364.1 and DE 199 14 363.1 (Henkel KGaA) described. The particulate machine dishwashing detergent disclosed there contain builders and optionally other ingredients from the groups of surfactants, Enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, color and Fragrances as well as a certain rinse aid in particular Composition. However, a particle size is necessary for the functioning of the invention of the rinse aid is necessary to pump out the rinse aid particles in the intermediate rinse cycle prevented. Due to the different size of the powder matrix and rinse aid particles segregation can occur, which gives the advantages when dosing powder detergents should be kept since they are not always the same Amounts of detergent and rinse aid are dosed.

The present invention was based on the object, the advantages of controlled clearance setting of ingredients, especially a rinse aid, also for powdery Make detergents usable without additional problems such as segregation etc. to generate. The use of nonionic surfactants in large quantities should also be avoided become. In addition, complex process steps such as coating or more should be applied compartment coating can be dispensed with.

It has now been found that the use of nonionic surfactants and in particular nonionic surfactants mix powdered machine dishwashing in certain quantity ranges gives a rinse aid effect without the additional use of rinse aid occurs in the rinse aid.

The present invention relates to particulate machine dishes detergent, the content of nonionic surfactants 5 to 25 wt .-%, each based on the entire average.

Surprisingly, the cleaning agents according to the invention, despite the multiple fa water change in the normal household machine and despite smaller quantities  Nonionic surfactant rinse aid results, the performance of the conventional combination "powder + Rinse Aid ".

The one remaining in the machine after the main wash and the intermediate wash cycles Amounts of surfactants cause an adequate drainage behavior in the rinse aid, so that the water draining from the wash ware leaves no stains on drying. The rinse aid gang does not need additional deliberately when using the agents according to the invention added rinse aid.

Usually only surfactants are used in automatic dishwashing detergents low-foaming nonionic surfactants are used. Representatives from the groups of By contrast, anionic, cationic or amphoteric surfactants are of less importance. The nonionic surfactants, which according to the invention in amounts of 5 to 25 wt .-% in the Means included are described below.

In particularly preferred embodiments of the present invention, the cleaning agent according to the invention contains nonionic surfactants from the group of the alkoxylated alcohols. Such nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols, preferably having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a linear or preferably 2-methyl branching may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred nonionic surfactants, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alka nolamides may be suitable. The amount of these nonionic surfactants is before preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in the RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for water, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups . The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compounds can then be reacted with fatty acid methyl esters in the presence of an alkoxide as catalyst in the desired Polyhydroxy fatty acid amides are transferred.

It is with the cleaning agents according to the invention for machine dishwashing particularly preferred that they contain a nonionic surfactant that has a melting point above room temperature. Here are particulate machine dishwashers medium preferred, the nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and  in particular between 26.6 and 43.3 ° C, in amounts of 5.5 to 20 wt .-%, preferably from 6.0 to 17.5% by weight, particularly preferably from 6.5 to 15 and in particular from 7.0 to 12.5 wt .-%, each based on the total agent.

Suitable nonionic surfactants, the melting or softening points in the above Temperature range are, for example, low-foaming nonionic ten side, which can be solid or highly viscous at room temperature. Will be at room temperature rature highly viscous nonionic surfactants used, it is preferred that these have a viscosity above half of 20 Pas, preferably above 35 Pas and in particular above 40 Pas exhibit. Also non-ionic surfactants, which have a waxy consistency at room temperature, are preferred.

Preferred nonionic surfactants to be used as solid at room temperature originate from the group pen of the alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and Mixtures of these surfactants with structurally more complex surfactants such as Po lyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has emerged. Corresponding particulate machine dishwashing detergents, which are characterized in that the nonionic surfactant (s) is / are ethoxylated nonionic surfactant (s), which / which consist of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _{16 -20} -fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol, are accordingly preferred.

A particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide won. Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, in particular more preferably up to 20% by weight and in particular up to 15% by weight of the total moles mass of the nonionic surfactant. Particulate dishwasher detergents, which contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxides are units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant is before preferred embodiments of the present invention. Particularly preferred nonioni cal surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally Have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or Alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a polyoxypropy len / polyoxyethylene / polyoxypropylene block polymer blends, the 75 wt .-% of a vice returned block copolymers of polyoxyethylene and polyoxypropylene with 17 moles of ethyl lenoxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of Po lyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles Ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

Nonionic surfactants, which can be used with particular preference, are from for example under the name Poly Tergent® SLF-18 from Olin Chemicals true.

Another preferred surfactant can be represented by the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ]

describe in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1 , 5 and y stands for a value of at least 15. Particulate machine dishwashing detergents, which are characterized in that they are nonionic surfactants of the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ]

contain, in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1 , 5 and y stands for a value of at least 15 are therefore preferred.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≧ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≧ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R ³ group can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO ) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO ) (PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa.

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particular preference is given to surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15.

In summary, particulate machine dishwashing detergents are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

contain, in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, isopropyl , n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, surfactants of the type

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18 stands, are particularly preferred.

Mixtures of different nonionic surfactants are particularly preferably used in the particulate dishwashing detergents according to the invention. Particulate machine dishwashing detergents which have a content of

• a) 1.0 to 4.0 wt .-% nonionic surfactants from the group of alkoxylated alcohols get,
• b) 4.0 to 24.0% by weight of nonionic surfactants from the group of the hydroxyl groups containing alkoxylated alcohols ("hydroxy mixed ethers").

exhibit.

The nonionic surfactants from group a) have already been described in detail above, with particular reference being made to machine dishwashing detergents which contain the mixtures mentioned above, especially C _12-14 fatty alcohols with 5 EO and 4 PO and C _12-18 - Fatty alcohols with an average of 9 EO have proven to be outstanding. End group-sealed nonionic surfactants, in particular C _12-18 fatty alcohol-9 EO-butyl ether, can also be used with a similar preference.

Surfactants from group b) show outstanding rinse aid effects and reduce the span Corrosion cracking on plastics. Furthermore, they have the advantageous property that their network behavior is constant over the entire usual temperature range. The surfactants from group b) are particularly preferably alkoxy containing hydroxyl groups gated alcohols, as described in EP 300 305, the disclosure of which here is expressly accepted. All hydroxy mixed ethers disclosed there are off without exception with preference as surfactant from group b) in the preferred according to the invention Dishwashing detergent included.  

The amounts in which the surfactants from groups a) and b) can be present in dishwashing detergents preferred according to the invention vary depending on the desired product and are preferably within narrow ranges. Particularly preferred particulate machine dishwashing detergents contain

• a) 1.5 to 3.5 wt .-%, preferably 1.75 to 3.0 wt .-% and in particular 2.0 to 2.5% by weight of nonionic surfactants from the group of the alkoxylated alcohols,
• b) 4.5 to 20.0% by weight, preferably 5.0 to 15.0% by weight and in particular 7.0 to 10.0% by weight of nonionic surfactants from the group of hydroxyl-containing ones alkoxylated alcohols ("hydroxy mixed ethers").

The introduction of the nonionic surfactant (s) into the agents according to the invention can done in different ways. The surfactants can, for example, in molten Condition sprayed onto the otherwise ready-made agent or with the tel in the form of compounds or surfactant preparation forms. Especially it is preferred to use particulate dishwashing detergents with high-surfactant particles called "rinse aid particles" to add.

Another object of the present invention is therefore a particulate ma machine dishwashing detergent, containing builders and optionally other ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, dyes and fragrances, which is characterized in that it is a partly contains rinse aid in the form of a dish, based on its weight

• a) 20 to 90 wt .-% of one or more carrier materials from the group of Ge builders,
• b) 10 to 40% by weight of one or more nonionic surfactants and
• c) 0 to 70% by weight of further active ingredients and auxiliaries,

contains.

Particularly preferred particulate machine dishwashing detergents are thereby characterized in that the particulate rinse aid as carrier (e) a) one or more Substances from the groups of phosphates, carbonates, hydrogen carbonates and / or silicates in Amounts from 25 to 85% by weight, preferably from 35 to 82.5% by weight and in particular  from 45 to 80% by weight, based in each case on the weight of the particulate rinse aid, contains. These substances are described below.

Among the phosphates, the alkali metal phosphates are again particularly preferred as carrier materials for the rinse aid particles. Alkali metal phosphates is the overall term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues, and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to pH 4.5 with caustic soda and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when He's heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] that crystallizes with 6 H ₂ O. _n -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 20 ° approx. 20 g, at 100 ° around 32 g of the salt free of water; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these phosphates are exactly like sodium tripolyphosphate and potassium tripoly phosphate or mixtures of these two can be used; also mixtures of sodium tri polyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripoly phosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate are one in the present invention settable.

Other ingredients that replace or in addition to phosphates as carrier materials Can be used are carbonates and / or hydrogen carbonates, the Alka limetal salts and among them especially the potassium and / or sodium salts are preferred. Preferred particulate detergents contain carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in Amounts from 25 to 75% by weight, preferably from 30 to 60% by weight and in particular  from 35 to 50% by weight, based in each case on the mass of the rinse aid contained in them particle.

Other ingredients instead of or in addition to the phosphates mentioned and / or carbonates / bicarbonates in the cleaning agents according to the invention can be included are silicates, with the alkali metal silicates and below in particular the amorphous and / or crystalline potassium and / or sodium disilicate are preferred.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .y H ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline ranges of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdry X-ray amorphous silicates.

The particulate cleaning agents according to the invention can be used as carrier materials or also contain zeolites in the remaining solid matrix, preferred means not Nene zeolite as carrier material in the rinse aid particles and particularly preferred agents contain no zeolite at all.

Zeolites have the general formula

M _{2 / n} O.Al ₂ O ₃ .x SiO ₂ .y H ₂ O

where M is a cation of valence n, x stands for values that are greater than or equal to 2 and y can assume values between 0 and 20. The zeolite structures are formed by linking AlO ₄ tetrahedra with SiO ₄ tetrahedra, this network being occupied by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged for other cations in different degrees. The intercrystalline "zeolitic" water can be released continuously and reversibly depending on the type of zeolite, while for some types of zeolite structural changes are also associated with the water release or absorption.

In the structural subunits, the "primary binding units" (AlO ₄ tetrahedra and SiO ₄ tetrahedra) form so-called "secondary binding units", which have the form of one or more rings. For example, 4-, 6- and 8-membered rings appear in different zeolites (referred to as S4R, S6R and S8R), other types are connected via four- and six-membered double ring prisms (most common types: D4R as a square prism or D6R as a hexagonal prism ). These "secondary subunits" combine different polyhedra, which are denoted by Greek letters. The most common is a polyhedron, which is made up of six squares and eight equilateral hexagons and is referred to as "β". A variety of different zeolites can be realized with these units. To date, 34 natural zeolite minerals and around 100 synthetic zeolites are known.

The best known zeolite, zeolite 4A, is a cubic assembly of β-cages linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 Å and 4.2 Å in size, the formula unit in the unit cell can be expressed with Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]. 27 H ₂ O describe.

If zeolites are used, faujasite-type zeolites are preferably used. Together with the zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which by the double six-ring subunit D6R (see Donald W. Breck: "Zeolite Molecular Sieves", John Wi ley & Sons, New York, London, Sydney, Toronto, 1974, page 92). To the zeolite In addition to the faujasite types mentioned, structure group 4 also includes the minerals Chaba zit and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral Analogues.

Faujasite-type zeolites are composed of β-cages, which are linked tetrahedrally via D6R subunits, the β-cages being arranged similarly to the carbon atoms in the diamond. The three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 Å, the unit cell also contains 8 cavities with a diameter of approx. 13 Å and can be determined by the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .264 H ₂ O. The network of Zeo lith X contains a void volume of approximately 50%, based on the dehydrated crystal, which is the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume). (All data from: Do nald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).

In the context of the present invention, the term "zeolite from faujasite Type "all three zeolites that form the faujasite subgroup of zeolite structure group 4. In addition to zeolite X, zeolite Y and faujasite as well as mixtures are therefore also according to the invention  of these compounds can be used according to the invention, the pure zeolite X is preferred.

Mixtures or cocrystallizates of zeolites of the faujasite type with other Zeo Lithen that do not necessarily have to belong to zeolite structure group 4 are invented usable according to the invention, the advantages of the method according to the invention being particularly great emerge clearly when at least 50 wt .-% of the powdering agent from a Faujasite type zeolites exist. It is also conceivable, for example, that the mini Male amount of a faujasite type zeolite (0.5 wt .-%, based on the weight of the resulting molding) is used and conventional as the remaining powdering agent Zeolite A used. However, it is preferred in any case that the powdering agent is made of finally consists of one or more zeolites of the faujasite type, with zeolite X is again preferred.

The aluminum silicates used in the cleaning agents according to the invention are commercially available and the methods for their presentation are standard monographs described.

Examples of commercially available X-type zeolites can be described by the following formulas:

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,

K ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,

Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,

Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,

in which x can have values between 0 and 276 and the pore sizes from 8.0 to 8.4 Å exhibit.  

A co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is available from CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through the formula

n Na _20. (1-n) K ₂ O. Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

can be described.

Y-type zeolites are also commercially available and can be expressed, for example, by the formulas

Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] .x H ₂ O,

K ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] .x H ₂ O,

in which x stands for numbers between 0 and 276 and have a pore size of 8.0 Å, describe.

The above-mentioned builder substances can be used as carrier materials in the Klar Dishwasher particles are included, but they can also be additional or only Be be part of the "remaining" particulate detergent.

The cleaning agents according to the invention contain the second constituent of the rinse aid particles agent non-ionic surfactant (s), which have already been described in detail above were. Also in the event that the cleaning agents according to the invention the Nioten sid (e) in the form of separate rinse aid particles are particulate machine Dishwashing detergent preferred, in which the particulate rinse aid as nonionic Surfactants b) Mixtures of alkoxylated alcohols and hydroxy mixed ethers in quantities from 10 to 35% by weight, preferably from 10.5 to 30% by weight and in particular from 11 to Contains 20 wt .-%, each based on the weight of the particulate rinse aid.  

The particulate cleaning agents according to the invention can contain further ingredients contain, either localized as active or auxiliary substances in the rinse aid particles or otherwise incorporated into the funds. These substances are listed below described and can each as further active ingredients or auxiliary substances in the rinse aid parties included, but they can also be an additional or only part of the be "other" particulate detergent.

When rinse aid particles are used, particulate machine-like ones are according to the invention Dishwashing detergent preferred, in which the particulate rinse aid as a further active and / or auxiliaries c) one or more substances from the groups of dyes, fragrances, Defoamers, polymers, scale inhibitors, silver preservatives, enzymes and / or Mi from this in amounts of 5 to 60% by weight, preferably 10 to 50% by weight and in particular from 15 to 30% by weight, in each case based on the weight of the particle shaped rinse aid.

In addition to the substances mentioned above, bleaches, bleach activators, co builder, cheat and complexing agent, water softening substances, acidification and / or alkalizing agents as well as setting, separating and anti-caking agents as components of the agents according to the invention preferred. In the case of the first three substances it is an advantage not to incorporate them into the rinse aid particles.

In summary, particulate machine dishwashing detergents are preferred which are characterized in that they continue to contain one or more substances from the group Pen of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, coatings inhibitors, cobuilder dyes and / or fragrances in amounts of 25 to 70 wt .-%, before preferably from 30 to 60% by weight and in particular from 40 to 50% by weight, in each case based on on the weight of the entire composition.

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. "Sodium percarbonate" is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ .3 H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 that easily disintegrates into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a Obtained solution of sodium carbonate in hydrogen peroxide, but mistakenly as peroxy viewed carbonate. It was not until 1909 that the compound was Addition compound recognized, nevertheless the historical designation "sodium per carbonate "is established in practice. The bulk density of the finished product can vary vary between 800 and 1200 g / l after the manufacturing process. Usually it will Percarbonate stabilized by an additional coating. Coating process and substances that are widely used in the patent literature. Reason all commercial percarbonate types can additionally be used according to the invention such as those from the companies Solvay Interox, Degussa, Kemira or Akzo Tobe offered.

Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium ses quicarbonate is preferred, regardless of what other ingredients are included in the agents. Bleaching agents from the group of organic bleaching agents can also be used in the agents according to the invention. Typical organic bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxy acid perooxyperaproic acid (ε-phthalimidoperoxyiminoproic acid) , N-nonenylamidoperadipic acid and N- nonenylamidopersuccinates)], o- Carboxybenzamidoperoxycapronsäure, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, Diper oxybrassylsäure, the diperoxyphthalic acids, 2-decyldiperoxybutane-1 , 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents. Suitable chlorine or bromine releasing materials include, for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

To be a better choice when washing or cleaning at temperatures of 60 ° C and below To achieve the greatest bleaching effect, bleach activators can be incorporated. Pale Activators that support the effect of the bleaching agents are, for example, compounds gene containing one or more N- or O-acyl groups, such as substances from the Class of anhydrides, esters, imides and acylated imidazoles or oximes. At Games are Tetraacetylethylenediamine (TAED), Tetraacetylmethylenediamine (TAMD) and Tetraacetylhexylene diamine (TAHD), but also pentaacetyl glucose (PAG), 1,5-diacetyl 2,2-dioxohexahydro-1,3,5-triazine (DADHT) and isatoic anhydride (ISA).

As bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acid are used become. Substances which contain O- and / or N-acyl groups of the C- Bear atomic number and / or optionally substituted benzoyl groups. Are preferred multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates,  in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and enol esters as well acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N- Benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams also preferably used. Combinations of conventional bleach activators can be used.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated. These substances are to bleach-enhancing transition metal salts or transition metal complexes as in for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Bleach activators from the group of multi-acylated alkylene are preferred diamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N- Nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight up to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight on the entire medium.

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

Further preferred cleaning agents are characterized in that they protect against silver medium from the group of triazoles, benzotriazoles, bisbenzotriazoles, Ami notriazole, the alkylaminotriazole and the transition metal salts or complexes, esp preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably from 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, in each case based on total mean.

The corrosion inhibitors mentioned can protect the wash ware or the size machine are also incorporated into the masses to be processed, in the area of machine dishwashing silver protection agents have a special meaning. The known substances of the prior art can be used. Generally can before all silver protection agent selected from the group of triazoles, benzotriazoles, Bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salt ze or complexes are used. Benzotria are particularly preferred zole and / or alkylaminotriazole. One also finds in cleaner formulations agents containing active chlorine, which significantly reduce the corroding of the silver surface can. Chlorine-free cleaners especially contain oxygen and nitrogen organic redox-active compounds, such as di- and trihydric phenols, e.g. B. Hydro quinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or Derivatives of these classes of compounds. Also salt and complex inorganic compound Applications such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. The transition metal salts which are selected from the group of Manganese and / or cobalt salts and / or complexes, particularly preferably the Cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, chlorides of cobalt or manganese and manganese sulfate. You can also Zinc compounds are used to prevent corrosion on the wash ware.  

Enzymes in particular come from the hydrolase classes such as the protea sen, esterases, lipases or lipolytically acting enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal stains such as protein, fat or starchy stains. For Bleach can also be used with oxidoreductases. Are particularly well suited Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified adorned variants obtained enzymatic agents. Proteases are preferred of the subtilisin type and in particular proteases obtained from Bacillus lentus, used. Enzyme mixtures, for example of protease and amylase or Protease and lipase or lipolytic enzymes or from protease, amylase and Lipase or lipolytic enzymes or protease, lipase or lipolytic we enzymes, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. examples for Such lipolytic enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases. To the appropriate ones Amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectina sen.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight, based in each case on the total agent.

Other ingredients that can be part of the agent according to the invention are in for example cobuilders, dyes, fragrances, soil release compounds, soil repellents, Antioxidants, fluorescent agents, foam inhibitors, silicone and / or paraffin oils, etc. These substances are described below.

Usable organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, with such carboxylic acids under polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid,  Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adi Pinic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of the sen.

The acids themselves can also be used. The acids have besides their buil the effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{W of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.  

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As a special copolymers of acrylic acid with maleic acid, 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative mole Cooling mass, based on free acids, is generally from 2000 to 70,000 g / mol preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The content of (co) polymeric polycarboxylates in the agent is before preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer ten.

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.

Further preferred copolymers are those which preferably contain acrolein as monomers and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyas are particularly preferred Paraginic acids or their salts and derivatives, which in addition to cobuilder properties have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehyden with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl have groups that can be obtained. Preferred polyacetals are made from dialdehydes  such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is a poly saccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenedia mindisuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and Gly are also preferred in this context cerintrisuccinate. Suitable amounts are in zeolite and / or silicate salts gene formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarbon acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and maxi contain two acid groups.  

Another class of substances with cobuilder properties are the phosphonates it is in particular hydroxyalkane or aminoalkanephosphonates. Under the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Ho mologist in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, used. HEDP is preferred as a builder from the phosphonate class turns. The aminoalkanephosphonates also have a pronounced heavy metal bin de assets. Accordingly, it can, especially if the agent also ent bleach hold, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth train ions as cobuilders.

In order to improve the aesthetic impression of the agents according to the invention, they can completely or partially (e.g. only the rinse aid particles) colored with suitable dyes become. Preferred dyes, the selection of which no difficulty for the expert prepares, have a high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity against over the treated substrates such as dishes, so as not to turn them on to dye.

When choosing the colorant, care must be taken that the colorants do not have too strong an affinity for the surfaces. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stability to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the cleaning agents varies. In the case of readily water-soluble colorants, e.g. B. Basacid® Green or Sandolan® Blue, colorant concentrations in the range from a few 10 ^-2 to 10 ^-3 wt .-% are typically selected. In the particular preferred due to their brilliance, but less water-soluble pigment dyes, for. B. the Pigmosol® dyes, the suitable concentration of the colorant in washing or cleaning agents, however, is typically around 10 ^-3 to 10 ^-4 wt .-%.

Fragrances are added to the agents according to the invention in order to maintain an aesthetic appearance to improve product pressure and consumer in addition to product performance a visually and sensorially "typical and distinctive" product is available put. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and Koh type Hydrogen oils are used. Fragrance compounds of the ester type are e.g. B. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dime thylbenzyl-carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the Ethers include, for example, benzyl ethyl ether, the aldehydes e.g. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝- Isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, are hydrocarbons mainly the terpenes such as limes and pinene. However, Wed are preferred uses different fragrances, which together make an appealing Generate fragrance. Such perfume oils can also contain natural fragrance mixtures ten, as they are accessible from plant sources, e.g. B. Pine, Citrus, Jasmine, Pat chouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Ka millen oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.  

The fragrance content of the cleaning agents according to the invention is usually up to to 2% by weight of the total formulation. The fragrances can be used directly in the invention appropriate agents can be incorporated, but it can also be advantageous to apply the fragrances Apply carriers that increase and adhere the perfume to the laundry a slower fragrance release ensures a long-lasting fragrance of the textiles. As such Carrier materials have proven themselves, for example, cyclodextrins, the Cyclodex trin-perfume complexes can also be coated with other auxiliaries nen.

As foam inhibitors that can be used in the agents according to the invention, For example, soaps, paraffins or silicone oils come into consideration, which if necessary can be applied to carrier materials.

To combat microorganisms, the agents according to the invention can be antimicro bielle contain active ingredients. A distinction is made here depending on the antimicrobial spectrum and mechanism of action between bacteriostatics and bactericides, fungiostatics and Fungicides, etc. Important substances from these groups are, for example, benzalkonium chloride, alkylarlyl sulfonates, halophenols and phenol mercuric acetate, whereby also complete Lich these connections can be dispensed with.

To unwanted, caused by oxygen and other oxidative processes To prevent changes to the agents, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, Catechnins and aromatic amines as well as organic sulfides, polysulfides, dithiocar bamates, phosphites and phosphonates.

An increased ease of use for the treated surfaces can result from the additional Use of antistatic agents result, the agents produced according to the invention can also be added. Antistatic agents increase the surface conductivity and he possible an improved drainage of charges formed. External antistatic agents are usually substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These are mostly surface-active  Antistatic agents can be broken down into nitrogen-containing (amines, amides, quaternary Am monium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl divide sulfonates, alkyl sulfates) antistatic agents.

All of the ingredients mentioned above can have advantageous properties result in separating them from other ingredients or combining them with certain others To assemble ingredients together.

An advantage of the present invention is that the rinse aid particles are in each Size can be made and no consideration for the sieve size of the lye sump sieve must be taken because the particles do not have to be prevented from pumping sen. Separation problems due to large particles in a matrix of smaller particles or dosing problems due to overall enlarged particles can be avoided.

Preferred particulate machine dishwashing detergents are characterized in that that the particulate rinse aid particle sizes between 400 and 2000 microns, preferred has between 600 and 1800 microns and in particular between 800 and 1600 microns.

The particle size of the entire detergent (including the rinse aid particles, if these exist are also on this scale. Preferred particulate ma Rapid dishwashing detergents are characterized in that they have particle sizes between 200 and 3000 µm, preferably between 300 and 2500 µm and in particular has between 400 and 2000 microns.

The above information on particle sizes relate to the absolute ranges, inner half of which are at least 95% by weight of all particles. Small amounts of fine or oversize particles influence the particle size of the agent within the scope of this definition tion not.

Are the cleaning agents according to the invention as a powder mixture with varying Formulated particle sizes, although this is not preferred, can be - in particular with very different sizes of rinse aid particles and detergent matrix -  on the one hand partial separation occurs when the package is shaken, on the other hand the dosage can be different in two successive cleaning cycles, since the consumer does not always have the same amount of detergent and rinse aid dosed. If desired, technically always the same amount per cleaning use, this can be done via the packaging of the inventor familiar to the person skilled in the art Agents according to the invention can be realized in bags made of water-soluble film. Also part Chen-shaped machine dishwashing detergent, in which a dosing unit in a bag welded from water-soluble film is the subject of the present invention dung.

Another object of the present invention is a method for producing powdered machine dishwashing detergent with rinse aid effect, in which a powdered machine dishwashing agent known per se with rinse aid particles

• a) 20 to 90 wt .-% of one or more carrier materials from the group of Ge builders,
• b) 10 to 40% by weight of one or more nonionic surfactants and
• c) 0 to 70% by weight of further active ingredients and auxiliaries,

each based on the weight of the particulate rinse aid, is mixed.

Regarding the preferred amounts of the ingredients of the particulate dishes detergent and the rinse aid particles as well as preferred representatives from the individual substance classes, reference is made to the above explanations, the mutatis mutandis also apply to the method according to the invention.

The rinse aid particles can be produced, for example, by customary granulation processes ren done. For this purpose, the ingredients a) are placed in a mixer and mixed with the Ingredients b) mixed / granulated, in the case of several surfactants used these can be added either together or in succession. Will then If powdered material is added ("powdered"), the powder can be mixed significantly improve the properties of the rinse aid particles. Can be used as a powdering agent  the known substances of the prior art are used in the context of In particular, the present invention has proven to be particularly advantageous sen.

However, other finely divided substances, such as those from group a) such as soda, are also suitable or phosphate, or over-dried water glasses, ground ingredients from Reini agents, etc.

The compositions according to the invention can be used in all household dishes dishwashers are used, but there is no limit to the choice of program exist. The beneficial effects are both in low temperature programs such as 45 ° C programs or glass programs as well as at 50/55 ° C or 60/65 ° C Programs achieved.

Another object of the present invention is therefore a method for cleaning of dishes in a household dishwasher, in which an inventive part Chen-shaped machine dishwashing detergent in the main wash of the machine is introduced.

The introduction into the main cleaning cycle can be done by filling the dosing chamber done with the powder, opening the dosing chamber after a possible Pre-cleaning the powder is released into the machine. Alternatively, it is possible to bring the powder directly into the machine and in this way already in release an active substance in an optional pre-cleaning cycle. Alternatively, you can click on a pre-cleaning cycle can be dispensed with. By means of the invention no additional rinse aid should be dispensed in the rinse aid cycle. Me according to the invention methods in which the rinse cycle of the machine without the deliberate addition of further Rinse aid is therefore preferred.

The term "further rinse aid" includes liquid commercial rinse aid medium, the consumer at intervals of several rinsing cycles in a storage container Machine must be given and released from there under program control. This intentional addition of a rinse aid and the second dosing step required for this  at intervals of a few rinsing cycles through the use of the invention tel not required.

Another object of the present invention is a method for cleaning dishes in a household dishwasher using particulate machine dishwashing detergent, comprising the steps

• a) Contacting the soiled wash ware with an aqueous cleaning liquor Water and the particulate machine dishwashing detergent, the part Chen-shaped automatic dishwashing detergent 5 to 25 wt .-% non-ionic Ten sid (e) contains
• b) Pump out the cleaning liquor and contact the wash ware with a Klar rinse cycle.

As already mentioned, the advantages of the present invention are also achieved if the main wash cycle and rinse cycle are interrupted by intermediate rinse cycles will be. Preferred methods are therefore characterized in that between the Steps a) and b) one or more intermediate rinse cycles.

Again, the additional deliberate dosage of commercial rinse aid is not required, so that methods are preferred in which no further clarification in step b) Dishwasher is added deliberately.

Examples

Granulation in a 130 liter ploughshare mixer from Lödige made it clear Dishwasher particles produced in the composition shown in Table 1.

Table 1

Rinse aid particles [% by weight]

The rinse aid particles were removed by removing coarse fractions on a grain spectrum brought from 800-1600 microns and then a powdered dish detergent added. The composition of the finished product is shown in Table 2.

Table 2

Dishwashing detergent [% by weight]

Performance evaluation

To evaluate the rinse aid effect and the drying behavior, a commercially available ch powder detergent for automatic dishwashing in a universal Cleaning program used. The program was run under the same conditions conditions once without standard rinse aid (storage tank of the dishwasher emptied), with commercially available rinse aid (dosage of 3 ml of commercial rinse aid ler from the storage tank in the rinse cycle) and once with the agents according to the invention, contain the rinse aid particles (20 g detergent, dosage before the main wash) leads. When using the cleaning agents according to the invention, the storage tank for the commercial rinse aid of course empty, d. H. the rinse aid is only on the in the rinse aid particles contained in the agents according to the invention.

Test conditions

Dishwasher: Miele G 676
Detergent: 20 g, dosed in the main wash
Water hardness: 3 ° dH
Program: Universal 65 ° C (rinse aid temperature 70 ° C)
Dirt load: 50 g liquid dirt, dosed in the main wash cycle.

composition

30% protein
30% strength
30% fat
10% water / emulsifier.

The rinse aid effect (KSE) was assessed by visual inspection of the Ob objects in a box, the walls of which are lined with black velvet, the Grades 0 to 8 were awarded; the top grade 8 refers to free of deposits and water drops Surfaces. If the grade is ≦ 4, the deposits and drops are also outside the box clearly recognizable, d. H. they are perceived as disturbing by the consumer.

The drying (T) was assessed by counting the individual water drops on the wash ware in the above Box. The top grade 0 shows no drops, other values indicate how many drops are visible on the dishes. The given in the table below  Data are the mean values from 10 items of crockery that are in the be machine loading was included.

The table shows that the agents according to the invention by using the rinse aid par the rinse aid of the conventional combination of detergent and sepa achieve or even exceed advice on rinse aid to be dosed, although the inventive particles in the main wash cycle are already in the machine, i.e. physically and be chemically contaminated.

Claims (22)

1. Particulate automatic dishwashing detergent, characterized in that the nonionic surfactant content of the detergent is 5 to 25% by weight, in each case based on the total detergent. 2. Particulate dishwasher detergent according to claim 1, characterized records that it is nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, in amounts of 5.5 to 20 wt .-% before preferably from 6.0 to 17.5% by weight, particularly preferably from 6.5 to 15 and in particular contains from 7.0 to 12.5% by weight, each based on the total agent. 3. Particulate machine dishwashing detergent according to one of claims 1 or 2, characterized in that the nonionic surfactant (s) is / are ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _{6- 20} alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was obtained. 4. Particulate machine dishwashing detergent according to one of claims 1 to 3, characterized in that it contains ethoxylated and propoxylated nonionic surfactants, at which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15% by weight of the total molecular weight of the nonioni of surfactants. 5. Particulate machine dishwashing detergent according to one of claims 1 to 4, characterized in that it is nonionic surfactants of the formula
R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ]
contains, in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1 , 5 and y stands for a value of at least 15. 6. Particulate dishwasher detergent according to one of claims 1 to 5, characterized in that it is end-capped poly (oxyalkylated) nonionic surfactants of the formula
R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²
contains, in which R ¹ and R ² stand for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R ^{3 stands} for H or a methyl, ethyl, n-propyl, iso- Propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type
R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²
in which x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred. 7. Particulate dishwasher detergent according to one of claims 1 to 6, characterized by a content of

• a) 1.0 to 4.0% by weight of nonionic surfactants from the group of the alkoxylated alcohols,
• b) 4.0 to 24.0% by weight of nonionic surfactants from the group of the hydroxyl-containing alkoxylated alcohols ("hydroxy mixed ether").

8. Particulate dishwasher detergent according to claim 8, containing

• a) 1.5 to 3.5% by weight, preferably 1.75 to 3.0% by weight and in particular 2.0 to 2.5% by weight of nonionic surfactants from the group of the alkoxylated alcohols,
• b) 4.5 to 20.0% by weight, preferably 5.0 to 15.0% by weight and in particular 7.0 to 10.0% by weight of nonionic surfactants from the group of the hydroxyl-containing alkoxylated alcohols (" Hydroxy mixed ether ").

9. Particulate dishwasher detergent, containing builders and optional additional ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, dyes and fragrances, characterized in that it contains a particulate rinse aid based on its weight

• a) 20 to 90% by weight of one or more carrier materials from the group of builders,
• b) 10 to 40% by weight of one or more nonionic surfactants and
• c) 0 to 70% by weight of further active ingredients and auxiliaries,

contains. 10. Particulate machine dishwashing detergent according to claim 9, characterized records that the particulate rinse aid as carrier (e) a) one or more Substances from the groups of phosphates, carbonates, hydrogen carbonates and / or sili Kate in amounts of 25 to 85 wt .-%, preferably from 35 to 82.5 wt .-% and ins special from 45 to 80 wt .-%, each based on the weight of the particulate gene rinse aid. 11. Particulate machine dishwashing detergent according to claim 9, characterized records that the particulate rinse aid as nonionic surfactants b) mixtures of alkoxylated alcohols and hydroxy mixed ethers in amounts of 10 to 35% by weight, preferably from 10.5 to 30% by weight and in particular from 11 to 20% by weight, each based on the weight of the particulate rinse aid. 12. Particulate dishwasher detergent according to claim 9, characterized records that the particulate rinse aid as further active ingredients and / or auxiliary substances c) one or more substances from the groups of dyes, fragrances, defoamers, buttocks polymers, scale inhibitors, silver protection agents, enzymes and / or mixtures thereof in  Amounts from 5 to 60% by weight, preferably from 10 to 50% by weight and in particular from 15 to 30% by weight, based in each case on the weight of the particulate clear dishwasher, contains. 13. Particulate dishwasher detergent according to one of claims 9 to 12, characterized in that the particulate rinse aid has particle sizes between 400 and 2000 microns, preferably between 600 and 1800 microns and in particular between has between 800 and 1600 µm. 14. Particulate dishwasher detergent according to one of claims 1 to 13, characterized in that it has particle sizes between 200 and 3000 microns, preferred have between 300 and 2500 µm and in particular between 400 and 2000 µm has. 15. Particulate machine dishwashing detergent according to one of claims 1 to 14, characterized in that a dosing unit in a bag made of water-soluble The film is sealed. 16. Particulate dishwasher detergent according to one of claims 1 to 15, characterized in that it still contains one or more substances from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, coatings inhibitors, cobuilder dyes and / or fragrances in amounts of 25 to 70% by weight, preferably from 30 to 60% by weight and in particular from 40 to 50% by weight, in each case based on the weight of the entire composition. 17. A process for the production of powdered machine dishwashing detergents with a clear rinsing effect, characterized in that a known powdered machine dishwashing agent with rinse aid particles is known

• a) 20 to 90% by weight of one or more carrier materials from the group of builders,
• b) 10 to 40% by weight of one or more nonionic surfactants and
• c) 0 to 70% by weight of further active ingredients and auxiliaries,

each based on the weight of the particulate rinse aid, is mixed. 18. Method for cleaning dishes in a household dishwasher, thereby characterized in that a particulate machine dishwashing detergent after a of claims 1 to 16 is introduced into the main cleaning cycle of the machine. 19. The method according to claim 18, characterized in that the rinse aid of the Ma machine without the intentional addition of further rinse aid. 20. A method of cleaning dishes in a domestic dishwasher using particulate machine dishwashing detergents, comprising the steps

• a) contacting the soiled wash ware with an aqueous cleaning liquor composed of water and the particulate machine dishwashing detergent, the particulate machine dishwashing detergent containing 5 to 25% by weight of nonionic ten sid (s),
• b) Pumping out the cleaning liquor and contacting the wash ware with a rinse cycle.

21. The method according to claim 20, characterized in that between steps a) and b) one or more intermediate rinse cycles take place. 22. The method according to any one of claims 20 or 21, characterized in that in Step b) no further rinse aid is added intentionally.