EP1213344A2 - Cleaning or rinse composition for automatic dishwashing machines with odour absorbing component - Google Patents

Abstract

Use is claimed in machine dishwasher agents (especially those used in the rinsing stage) of non-alkali metal salts (I) of optionally unsaturated, mono- or poly-hydroxylated >= 8C fatty acids and/or of resin acids. Independent claims are also included for the following: (1) Rinsing agents containing (I). (2) Particulate rinsing agents comprising by wt. (I) (0.1-70%), together with: (a) carrier (0-65%), (b) covering material of melting point above 50[deg]C (30-70%), (c) fat(s) (0-65%) and (d) further active agents or aids (0-50%). (3) Builder-containing shaped bodies containing (I) at 0.5-60 (especially 5-30) wt.%. (4) Multi-phase shaped bodies composed as in (2). (5) A container which is hung in the dishwasher and which is (at least on one side) permeable to a composition containing (I).

Description

The present invention relates to machine dishwashing detergents and rinse aid for the machine dishwashing, which contain odor-absorbing substances.

The automatic cleaning of dishes in domestic dishwashers usually includes a pre-rinse, a main rinse and a rinse cycle that of intermediate rinse to be interrupted. On most machines, the pre-rinse cycle is for heavily soiled items Crockery can be switched on, but is only selected by the consumer in exceptional cases, so that in the Most machines have a main wash, an intermediate wash with pure water and a Rinse aid. The temperature of the main wash cycle varies depending on Machine type and program level selection between 40 and 65 ° C. In the rinse aid cycle, added a rinse aid to a dosing tank in the machine, usually called Main component contains non-ionic surfactants. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is Prevent limescale and deposits on the cleaned dishes. Besides water and weakly foaming nonionic surfactants often also contain hydrotopes, pH adjusters such as citric acid or scale-inhibiting polymers.

Today, machine-washed dishes are often subject to higher requirements than they are manually washed dishes. The same applies to the cleaning process, so that the machine dishwashing high demands are placed on cleanliness and hygiene.

So also one completely cleaned of food residues and of whitish ones, to water hardness or stains other dishes based on other mineral salts are then considered to be not perfect evaluated if the consumer smells unpleasant when opening the dishwasher perceives. To avoid these unpleasant smells, there are machine dishwashing detergents often perfumed in itself. But both with detergents and rinse aids the sometimes sensitive fragrances suffer from the drastic conditions in the rinse aid the dishwasher. As a result, it becomes uncomfortable for the consumer perceived "lye smell" insufficiently covered when opening the dishwasher.

The removal of unpleasant smells - also in dishwashers - is described in German patent application DE 199 37 871.1 (Henkel KGaA). It is proposed here to spray certain odor-absorbing compositions into the open dishwasher in order to bind the odors. However, this procedure requires a further application step by the consumer. In addition, the smell is first perceived and then eliminated, which is not a satisfactory solution from a consumer perspective.

As a further solution to this problem, international patent application WO 98/07812 (Procter & Gamble) proposes to incorporate fragrance release systems into automatic dishwashing detergents which contain β-keto esters of fragrance alcohols. These esters are slowly broken down and are supposed to create a long-lasting fragrance. Here, too, the esters are already partly split by the chemical and thermal stress in the main and rinse cycle, so that the sensitive fragrances are decomposed or pumped out with the rinse water before the rinse cycle. The proportion of fragrances that reaches the desired place of action is still low.

The storage tank in the dishwasher must be rinse-aid at regular intervals be filled, whereby one filling is sufficient for 10 to 50 rinse cycles, depending on the machine type. If you forget to fill the tank, glasses with limescale marks and Unsightly toppings. In the prior art, there are therefore some proposed solutions, one Integrate rinse aid into the detergent for machine dishwashing. This Proposed solutions are tied to the offer form of the compact molded body.

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

It was therefore still the task to provide funds that would make the uncomfortable Minimize or completely avoid "alkali smell" when opening the machine. To do this new rinse aids are made available with regard to the application properties deliver at least the same results as standard rinse aid and others Provide performance advantages, especially with regard to the problems mentioned above. The new rinse aid should be used both as a conventional rinse aid and in the form of Combination products can be used and theirs regardless of the form of preparation unfold advantageous properties. Last but not least, the use of the new rinse aid should also in conventional machine dishwashing detergents, i.e. the Funds should also provide performance benefits as an additional component.

It has now been found that the use of certain substances in cleaning agents for the automatic dishwashing brings about advantageous effects. It is particularly advantageous if these substances are used in the rinse aid.

The subject of the present invention is therefore the use in a first embodiment of metal salts of an unbranched or branched, unsaturated or saturated, one or polyhydric fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts, in automatic dishwashing detergents.

The mere addition of these compounds to cleaning agents has the effect that those with such agents treated dishes and machine surfaces have significantly less lye odor, as dishes that have been washed using conventional means. The effect is independent whether the machine dishwashing liquid, powder or in tablet form available.

As an additional positive effect, the drying time is reduced with that Detergent treated dishes, i.e. after the expiry of the Cleaning programs take the dishes out of the machine earlier and reuse them.

The invention features improved "cleanability" of the treated substrates later cleaning processes and by significantly reducing the drying time compared to comparable agents without the use of polymers containing sulfonic acid groups.

In the context of the teaching according to the invention, drying time is generally understood to mean the meaning, i.e. the time which elapses until a dish surface treated in a dishwasher is dried, but in particular the time which elapses, up to 90% of one with a cleaning or Rinse aid is dried in a concentrated or diluted form treated surface.

It is particularly advantageous if the metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 Carbon atoms and / or a resin acid with the exception of the alkali metal salts in the last Rinse cycle, i.e. are present in the rinse aid. In this way, the beneficial effect not weakened by subsequent rinses. Another object of the invention provides hence the use of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts, in the rinse cycle in the machine Dishwashing before.

According to the invention, one or more metal salts of one are used as the deodorant (s) unbranched or branched, unsaturated or saturated, single or multiple hydroxylated Fatty acid with at least 8 carbon atoms and / or a resin acid other than Alkali metal salts used.

One or more metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 10, preferably with at least 12 and in particular with at least 16 carbon atoms and / or a resin acid other than the alkali metal salts used. The salts of the longer chain Fatty acids or resin acids are usually more effective.

A preferred unbranched or branched, unsaturated or saturated, one or more The hydroxylated fatty acid with at least 16 carbon atoms is ricinoleic acid. A preferred one Resin acid is the abietic acid.

Preferred metals are the transition metals and the lanthanoids, especially those Transition metals of groups VIIIa, Ib and IIb of the periodic table as well as lanthanum, cerium and Neodymium, particularly preferably cobalt, nickel, copper and zinc, extremely preferably zinc. The Cobalt, nickel and copper salts and the zinc salts are equally effective However, the zinc salts are preferred for toxicological reasons.

In a preferred embodiment, one or more are accordingly Metal salts of ricinoleic acid and / or abietic acid, preferably zinc ricinoleate and / or Zincabietate, especially zinc ricinoleate, is used.

The effect of zinc ricinoleate is based on quenching odors, i.e. chemical bond of smelling substances, so that these are no longer perceptible by sensors, and distinguishes the principle of action of other deodorising systems such as odor-covering perfumes or the odor (substance) destroying biocides. According to today The state of knowledge is the odorants, so-called osmogens, for example low molecular weight Fatty acids, isovaleric acid, mercaptans, hydrogen sulfide, ammonia and thioethers, which in are generally good nucleophiles, complexed by the zinc ricinoleate and thereby the deprived of sensory perception. That is probably also important for the mechanism of action Hydroxyl group of ricinoleic acid, which is the ricinoleate anion in addition to the carboxylate group can also provide as a complex ligand.

The use according to the invention can be realized in a simple manner in that the mentioned substances in liquid, powdered or tableted cleaning agents or in Rinse aid should be incorporated.

In preferred embodiments of the present invention, the metal salts arrive in the Rinse cycle of machine dishwashing for use. Preferred others Embodiments of the present invention therefore relate to machine rinse aid Dishwashing and combination forms, the detergent and rinse aid connect with each other, the latter being offered in particular in powder or tablet form become.

Another preferred object of the present invention are rinse aid for the automatic dishwashing, containing metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 Carbon atoms and / or a resin acid with the exception of the alkali metal salts.

Such rinse aids are put into the storage tank of the dishwasher by the consumer given from where they are automatically dosed into the rinse aid. Depending on the dosing volume and The tank capacity is usually sufficient for one tank filling for 10 to 50 rinsing cycles.

Rinse aids preferred according to the invention contain the metal salt (s) in amounts of 0.1 to 20% by weight, preferably from 0.25 to 15% by weight and in particular from 0.5 to 10% by weight, each based on the rinse aid.

When choosing the amount of deodorant active ingredient component is the respective one Intended use to be taken into account as for a specific deodorant effect required amount depends on the type of odors to be eradicated. A reasonable amount leaves find out in a simple application test.

In one embodiment with a particular deodorant effect, the rinse aid according to the invention contains one or more deodorant active ingredients, preferably one or more metal salts of ricinoleic acid and / or abietic acid, in particular zinc ricinoleate and / or zinc abietate, particularly preferably zinc ricinoleate, in an amount of at least 2% by weight. %. The deodorizing effect is also given for the amounts mentioned below 2% by weight, but is sometimes judged by the user to be inadequate.
The agents according to the invention can also contain anionic, nonionic, cationic and / or amphoteric surfactants as the surfactant component, nonionic surfactants being preferred due to their foaming power.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained. Preferred sulfated Fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 Carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut- , Palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 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 can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly 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, C 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, either as the sole nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

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 alkanolamides can be suitable. The amount of these nonionic surfactants is preferably no longer than that of ethoxylated fatty alcohols, especially not more than half of them.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (IX),

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, 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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (X)

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

[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 be reacted with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

Low-foaming nonionic surfactants are used as preferred surfactants. The detergent components according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 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 can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly 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.

Rinse aids according to the invention which contain a nonionic surfactant which has a melting point above room temperature are particularly preferred. Accordingly, preferred rinse aids are characterized in that they contain 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.
Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used as solid at room temperature come from the groups of alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and mixtures thereof Surfactants with structurally complicated surfactants such as Polyoxypropylene / 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 is nonionic surfactant with a melting point above room temperature an ethoxylated nonionic surfactant, which from the Reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred nonionic surfactant which is solid at room temperature is obtained 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 , Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred rinse aids according to the invention contain 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 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the Molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene block copolymer units exhibit. The alcohol or alkylphenol part of such nonionic surfactant molecules is preferred 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. This makes them preferred rinse aids characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the Propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and make up in particular up to 15% by weight of the total molar mass of the nonionic surfactant, contain.

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Examples of nonionic surfactants that can be used with particular preference are available under the name Poly Tergent® SLF-18 from Olin Chemicals.

A further preferred rinse aid according to the invention contains 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 ], 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.

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, if x is 3, the radical R ³ 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 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 stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 carbon atoms, R ^{3 represents} H and x assumes values from 6 to 15.

If the latter statements are summarized, rinse aids according to the invention 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 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, 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 stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

In the context of the present invention, end-capped surfactants and nonionic surfactants with butyloxy groups can also preferably be used as nonionic surfactants. The first group includes representatives of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x R ² , in which R ^{1 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 C atoms, R ^{2 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 C atoms, which is optionally substituted with 1, 2, 3, 4 or 5 hydroxyl groups and optionally with further ether groups, R ³ for -H or methyl, ethyl, n- propyl, iso- propyl, n- butyl, iso- butyl or tert- butyl and x can have values between 1 and 40. R ² can optionally be alkoxylated, the alkoxy group preferably being selected from ethoxy, propoxy, butyloxy groups and mixtures thereof.

Preferred surfactants here are those in which R ^{1 is} a C _9-11 or C _11-15 alkyl radical, R ³ = H and x is from 8 to 15, while R ^{2 is} preferably a straight-chain one or branched saturated Alkrest stands. Particularly preferred surfactants can be represented by the formulas C _9-11 (EO) ₈ -C (CH _{3) 2} CH ₂ CH _3, C _11-15 (EO) ₁₅ (PO) ₆ -C _12-14 C _{9- 11} Describe (EO) ₈ (CH ₂ ) ₄ CH ₃ .

Mixed alkoxylated surfactants are also suitable, preference being given to those which have butyloxy groups. Such surfactants can be represented by the formula R ¹ (EO) _a (PO) _b (BO) _c describe in which R ^{1 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20, carbon atoms, a for values between 2 and 30, b for values between 0 and 30 and c stands for values between 1 and 30, preferably between 1 and 20.

Alternatively, the EO and PO groups in the above formula can also be interchanged, so that surfactants of the general formula R ¹ (PO) _b (EO) _a (BO) _c , in R ¹ for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical with 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c for values between 1 and 30, preferably between 1 and 20, can also be used with preference.

Particularly preferred representatives from this group of surfactants can be represented by the formulas C _9-11 (PO) ₃ (EO) ₁₃ (BO) ₁₅ , C _9-11 (PO) ₃ (EO) ₁₃ (BO) ₆ , C _{9- 11} (PO) ₃ (EO) ₁₃ (BO) _3, C _9-11 (EO) ₁₃ (BO) _{6, 9-} C ₁₁ (EO) ₁₃ (BO) _3, C _9-11 (PO) (EO) ₁₃ (BO) _3, C _9-11 (EO) ₈ (BO) _3, C _9-11 (EO) ₈ (BO) _2, C _12-15 (EO) ₇ (BO) _2, C _{11 9-} ( EO) ₈ (BO) ₂ , C _9-11 (EO) ₈ (BO). A particularly preferred surfactant of the formulas C _{13- 15} (EO) _9-10 (BO) _1-2 is commercially available under the name Plurafac® LF 221st A surfactant of the formula C _12-13 (EO) ₁₀ (BO) _{2 can also be used} .

Instead of the surfactants mentioned or in combination with them, cationic and / or amphoteric surfactants are used. In summary, rinse aids according to the invention preferred, the surfactant (s), preferably nonionic (s) surfactant (s) and in particular non-ionic surfactant (s) from the group of alkoxylated alcohols, in amounts from 0.1 to 60% by weight, preferably from 0.5 to 50% by weight, particularly preferably from 1 to 40% by weight, and in particular from 2 to 30% by weight, based in each case on the rinse aid.

Non-aqueous solvents which can be used in the agents according to the invention, come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or Glycol ethers, provided that they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, Glycol, propane or butanediol, glycerin, diglycol, propyl or butyl diglycol, hexylene glycol, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or Butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents, so that preferred rinse aid are characterized in that they are non-aqueous solvents, preferably ethanol, n-propanol, i-propanol, 1-butanol, 2-butanol, glycol, propanediol, butanediol, glycerin, diglycol, propyl diglycol, Butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, Methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, Propylene glycol t-butyl ether and mixtures of these solvents.

The rinse aids of the present invention may further contain hydrotropes. The addition such substances causes a poorly soluble substance in the presence of the hydrotrope, which itself is not a solvent, becomes water-soluble. Substances that improve solubility cause are referred to as hydrotropes or hydrotropes. Typical hydrotropes, e.g. in the The assembly of liquid washing or cleaning agents are xylene and cumene sulfonate. Other substances, e.g. Urea or N-methylacetamide, increase the solubility by structure-breaking effect, in which the water structure in the vicinity of the hydrophobic group a poorly soluble substance is broken down.

enthält, in der jeder der Reste R₁, R₂, R₃, R₄, R₅ unabhängig voneinander ausgewählt ist aus H oder einem C_1-5-Alkyl- oder -Alkenylrest und X für ein Kation steht.Rinse aids preferred in the context of the present invention contain solubilizers, preferably aromatic sulfonates of the formula

contains, in which each of the radicals R ₁ , R ₂ , R ₃ , R ₄ , R _{5 is} independently selected from H or a C _1-5 alkyl or alkenyl radical and X is a cation.

Preferred substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are independently selected from H or a methyl, ethyl, n -propyl-, iso -propyl-, n -butyl-, iso -butyl-, tert -butyl, n -pentyl, iso -pentyl or neo -pentyl radical. As a rule, at least three of the radicals R ¹ to R ^{5 mentioned are} hydrogen atoms, preference being given to aromatic sulfonates in which three or four substituents on the aromatic ring are hydrogen atoms. The remaining or the remaining two residues can take any position on the sulfonate group and each other. In the case of monosubstituted compounds of the formula I, it is preferred if the radical R _{3 is} an alkyl radical, while R ₁ , R ₂ , R ₄ and R _{5 are} H ( para substitution).
In the context of the present invention, particularly preferred aromatic sulfonates are toluene, cumene or xylene sulfonate.

Of the two industrially available toluenesulfonates ( ortho- and para- toluenesulfonate), the para- isomer is preferred for the purposes of the present invention. The para- isopropylbenzenesulfonate is also the preferred compound in the case of the cumene sulfonates. Since xylene is usually used industrially as a mixture of isomers, the commercially available xylene sulfonate is also a mixture of several compounds which result from the sulfonation of ortho-, meta- and para- xylene result. In these isomer mixtures, the compounds dominate in which the following radicals in the general formula I are methyl groups (all other radicals are H): R ₁ and R ₂ , R ₁ and R ₄ , R ₁ and R ₃ and R ₁ and R ₅ . In the case of the xylene sulfonates, at least one methyl group is therefore preferably ortho to the sulfonate group.
X in the general formula given above represents a cation, for example an alkali metal cation such as sodium or potassium. However, X can also represent the charge-equivalent proportion of a polyvalent cation, for example Mg ²⁺ / 2 or Al ³⁺ / 3, of which the sodium is preferred.

According to the invention, the sulfonates are preferably used in amounts of 0.2 to 10% by weight, preferably from 0.3 to 5% by weight and in particular from 0.5 to 3% by weight, in each case based on the rinse aid.

Acidifying agents can also be added to the rinse aid according to the invention in order to to lower the pH of the liquor in the rinse cycle. Both inorganic Acids as well as organic acids, provided that these are compatible with the other ingredients are. For reasons of consumer protection and handling safety, in particular the solid mono-, oligo- and polycarboxylic acids can be used. From this group again citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid are preferred, Fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as an acidifying agent in the context of Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and Adipic acid (max. 33% by weight). Rinse aid, the acidifying agent, preferably organic Acids with particular preference for adipic acid, amidosulfonic acid, succinic acid, Citric acid, fumaric acid, maleic acid, malonic acid, oxalic acid and tartaric acid as well Mixtures of these acids are preferred embodiments of the present Invention.

The rinse aid according to the invention can preferably additionally contain one or more substances from the groups of soil release polymers, dyes and fragrances. This are described in detail below.

The rinse aids described above are suitable for dosing via the storage tank commercial dishwashers. The preferred use of the invention mentioned metal salts can also be realized by delayed offer forms are provided by the consumer before the start of the cleaning cycle in the Dishwasher are dosed, but only release the active ingredients in the rinse aid. This has the advantage that the consumer only has to dose one product - instead of two.

a) 0 bis 65 Gew.-% eines oder mehrerer Trägermaterialien,

b) 30 bis 70 Gew.-% Hüllsubstanz(en) mit einem Schmelzpunkt oberhalb von 50°C,

c) 0 bis 65 Gew.-% Fettstoff(e),

d) 0 bis 50 Gew.-% weiterer Wirk- und/oder Hilfsstoffe sowie

e) 0,1 bis 70 Gew.-% an Metallsalzen einer unverzweigten oder verzweigten, ungesättigten oder gesättigten, ein- oder mehrfach hydroxylierten Fettsäure mit mindestens 8 Kohlenstoffatomen und/oder einer Harzsäure mit Ausnahme der Alkalimetallsalze

enthält.Another object of the present invention is also a particulate rinse aid for machine dishwashing, the

a) 0 to 65% by weight of one or more carrier materials,

b) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,

c) 0 to 65% by weight of fat (s),

d) 0 to 50% by weight of further active substances and / or auxiliaries and

e) 0.1 to 70 wt .-% of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts

contains.

All substances which are solid at room temperature are suitable as carrier substances a). Usually, you will select substances that have an additional effect in the cleaning process unfold, with builders being particularly suitable. In preferred carrier material-containing Particulate rinse aids are substances from the group of water-soluble rinsing agents Detergent and cleaning agent ingredients, preferably carbonates, bicarbonates, Sulphates, phosphates and the organic oligocarboxylic acids solid at room temperature in quantities from 35 to 60% by weight, preferably from 40 to 55% by weight and in particular from 45 to 50% by weight, each based on the particle weight.

The preferred carriers mentioned are described in detail below.

The particulate rinse aid can also be formulated without carrier materials and thus consist only of ingredients b) to e). Such components are manufactured in usually by shaping a melted mixture of ingredients. Rinse aid particles containing carrier material can be sprayed, sprayed or pour such a melt can be obtained on the support materials.

The manufacturing processes are described below; there follows a description of the Ingredients b) to d), the amounts given being based on carrier-free rinse aid particles Respectively. If carrier-based particles are to be produced, refer to the the following information on the composition of the mixture / melt on the carrier is applied, the proportion of the particle resulting from the proportions of the mixture and Carrier material in the particle results.

To the coating substances that are used in the rinse aid particles according to the invention different requirements, on the one hand the melting or Solidification behavior, but also the material properties of the coating in the solidified state, i.e. in the rinse aid particle. Because the rinse aid particles during transport or Storage should be permanently protected against environmental influences, the coating substance must high stability against, for example, shock loads occurring during packaging or transport exhibit. The coating substance should either be at least partially elastic or at least have plastic properties in order to respond to an impact caused by elastic or to react plastic deformation and not to break. The coating substance should have a melting range (Solidification range) in such a temperature range in which the enveloping active substances are not exposed to excessive thermal stress. on the other hand However, the melting range must be sufficiently high to at least slightly increase the temperature to still offer effective protection for the enclosed active substances. According to the invention the coating substances have a melting point above 30 ° C.

It has proven to be advantageous if the coating substance does not have a sharply defined melting point shows how it usually occurs with pure, crystalline substances, but under certain circumstances has a melting range spanning several degrees Celsius.

The coating substance preferably has a melting range which is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range is within the specified range Temperature interval occurs and does not indicate the width of the melting range. Preferably the width of the melting range is at least 1 ° C, preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C. without decomposition and which are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.
The waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, Shellac wax, whale, lanolin (wool wax), or pretzel fat, mineral waxes such as Ceresin or Ozokerite (earth wax), or petrochemical waxes like petrolatum, paraffin waxes or Microcrystalline waxes.

The chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrated jojoba waxes.

Synthetic waxes generally include polyalkylene waxes or polyalkylene glycol waxes Roger that. Compounds from other classes of material can also be used as covering materials meet the requirements regarding the softening point. As a suitable synthetic Compounds have, for example, higher esters of phthalic acid, in particular Dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG), proved. Synthetic waxes made from lower carboxylic acids and are also suitable Fatty alcohols, for example dimyristyl tartrate, which is sold under the name Cosmacol® ETLP (Condea) is available. Conversely, synthetic or semi-synthetic esters from lower alcohols are also included Fatty acids from native sources can be used. Tegin® 90, for example, falls into this class of substances (Goldschmidt), a glycerol monostearate palmitate. Also shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH) can be used according to the invention as a covering material.

The waxes, for example, are also included in the scope of the present invention so-called wax alcohols. Wax alcohols are high molecular weight, water-insoluble Fatty alcohols usually with about 22 to 40 carbon atoms. The wax alcohols are coming for example in the form of wax esters of higher molecular fatty acids (wax acids) as the main component many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), Cetyl alcohol, myristyl alcohol or melissyl alcohol. The wrapping of the invention coated solid particles can optionally contain wool wax alcohols, among which Triterpenoid and steroid alcohols, for example lanolin, understands that, for example, under the Trade name Argowax® (Pamentier & Co) is available. Also at least proportionately as Part of the envelope can be used in the context of the present invention Fatty acid glycerol esters or fatty acid alkanolamides, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.

The coating substance contained in the rinse aid particles according to the invention preferably contains predominant paraffin wax. That is, at least 50% by weight of the total contained enveloping substances, preferably more, consist of paraffin wax. Particularly suitable are paraffin wax contents (based on total coating substance) of about 60% by weight, about 70% by weight or about 80 wt .-%, with even higher proportions of, for example, more than 90 wt .-% particularly are preferred. In a particular embodiment of the invention, the total amount of used coating substance exclusively from paraffin wax.

Paraffin waxes show the other natural waxes mentioned within the scope of the present invention the advantage that in an alkaline detergent environment none Hydrolysis of the waxes takes place (as can be expected, for example, in the wax esters), because Paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially none Ingredients with a melting point of more than 70 ° C, particularly preferably of more than 60 ° C on. Shares of high-melting alkanes in the paraffin can fall below this Melting temperature in the detergent fleet undesirable wax residues on the cleaning surfaces or the goods to be cleaned. Such wax residues result usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided become.

Preferred particulate rinse aid contain at least one paraffin wax as the coating substance with a melting range from 50 ° C to 60 ° C.

The content of the paraffin wax used is preferably at ambient temperature (in which Rule about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax components are present in a wax at room temperature, the more useful it within the scope of the present invention. With increasing proportion of solid wax components increases the resilience of the rinse aid particles against impacts or friction on others Surfaces, which leads to a longer-lasting protection of the particles of active substances. High proportions of oils or liquid wax components can weaken the particles, which opens pores and the active substances to the environmental influences mentioned above get abandoned.

In addition to paraffin as the main constituent, the coating substance can also have one or more of the above mentioned waxes or wax-like substances. Basically, that should be the The mixture forming the coating substance must be such that the rinse aid particles are at least largely are insoluble in water. The solubility in water should be about 10 at a temperature of about 30 ° C Do not exceed mg / l and are preferably below 5 mg / l.

In any case, the coating should have the lowest possible solubility in water, even in water with elevated temperature, have a temperature-independent release of the Avoid active substances as much as possible.

The principle described above serves to delay the release of ingredients into one certain time in the cleaning cycle and can be used particularly advantageously if in the Main rinse with a lower temperature (for example 55 ° C) is rinsed so that the Active substance from the rinse aid particles only in the rinse aid cycle at higher temperatures (approx. 70 ° C) is released.

Preferred particulate rinse aids contain one or more substances as the coating substance a melting range of 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably of 7.5 up to 25% by weight and in particular from 10 to 20% by weight, in each case based on the particle weight, preference being given to particulate formulations which contain one or more substances with one as ingredient b) Melting range between 50 and 100 ° C, preferably between 52.5 and 80 ° C and in particular between 55 and 75 ° C, with paraffin waxes with a melting range of 50 ° C to 65 ° C and / or substances from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are preferred coating substances.

As a third ingredient, the particulate rinse aid according to the invention can be one or contain several fatty substances, preferred rinse aid being characterized in that it as ingredient c) 1 to 60, preferably 5 to 55, particularly preferably 10 to 50 and contain in particular 20 to 45 wt .-% fat (s).

Under fatty substances c) are liquid in the context of this application at normal temperature (20 ° C) to solid substances from the group of fatty alcohols, fatty acids and fatty acid derivatives, especially the fatty acid esters understood. Implementation products of fatty alcohols with Alkylene oxides and the salts of fatty acids are included in the scope of the present application the surfactants (see above) and are not fatty substances in the sense of the invention. Leave as fatty substances preferred according to the invention are fatty alcohols and fatty alcohol mixtures, fatty acids and Fatty acid mixtures, fatty acid esters with alkanols or diols or polyols, fatty acid amides, Use fatty amines etc.

Preferred detergent components contain one or more substances as ingredient c) from the groups of fatty alcohols, fatty acids and fatty acid esters.

The fatty alcohols that can be obtained from native fat and oils are, for example, alcohols 1-hexanol (capro alcohol), 1-heptanol (enant alcohol), 1-octanol (caprylic alcohol), 1-nonanol (pelargon alcohol), 1-decanol (capric alcohol), 1-undecanol , 10-undecen-1-ol, 1-dodecanol (lauryl alcohol), 1-tridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), 9 -cis-octadecen-1-ol (oleyl alcohol), 9-trans-octadecen-1-ol (erucyl alcohol), 9-cis-octadecen-1,12-diol (ricinol alcohol), all-cis-9,12-octadecadiene- 1-ol (linoleyl alcohol), all-cis-9,12,15-octadecatrien-1-ol (linolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 9-cis-eicosen-1-ol (gadoleyl alcohol), 5,8,11,14-eicosatetraen-1-ol, 1-heneicosanol, 1-docosanol (behenyl alcohol), 1-3-cis-docosen-1-ol (erucyl alcohol), 1-3-trans-docosen-1- ol (brassidyl alcohol) and mixtures of these alcohols. According to the invention, Guerbet alcohols and oxo alcohols, for example C _13-15 oxo alcohols or mixtures of C _12-18 alcohols with C _12-14 alcohols, can also be used without difficulty as fatty substances. However, it is of course also possible to use alcohol mixtures, for example those such as the C _16-18 alcohols prepared by Ziegler ethylene polymerization. Specific examples of alcohols which can be used as component c) are the above-mentioned alcohols and lauryl alcohol, palmityl and stearyl alcohol and mixtures thereof.

Particularly preferred detergent components according to the invention contain, as ingredient c), one or more C _10-30 fatty alcohols, preferably C _12-24 fatty alcohols, with particular preference for 1-hexadecanol, 1-octadecanol, 9-cis-octadecen-1-ol, all cis-9,12-octadecadien-1-ol, all-cis-9,12,15-octadecatrien-1-ol, 1-docosanol and mixtures thereof.

Fatty acids can also be used as ingredient c). Technically, most of these are obtained from native fats and oils by hydrolysis. While the alkaline saponification which was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as fatty substances in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. The use of is preferred in the context of the present compound Fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (trisacetic acid) and melissic acid (cerotic acid) 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t Linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid). Of course, tridecanoic acid, pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid can also be used. For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, as are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _{18 "),} palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt .-% C _12, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _{18 "),} tallow fatty acid (ca. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C _{16 '} , 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C _18' , 3% by weight C _{18 "} , 1% by weight C _18"' , hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight C ₁₆ , 2% by weight C ₁₇ , 63 wt .-% C _18: 1 wt .-% C _{18 '),} technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 parts by weight % C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 "} , 0.5% by weight C _18"' ), technical palmitin / stearic acid (approx. 1 wt% C ₁₂ , 2 wt% C ₁₄ , 45 wt% C ₁₆ , 2 wt% C ₁₇ , 47 wt% C ₁₈ , 1 % By weight C _{18 '} ) and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15 Ge % by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight C _{18 '} , 45% by weight C _{18 "} , 7% by weight C _18"' ).

The esters of fatty acids with alkanols, diols or polyols can be used as fatty acid esters use, with fatty acid polyol esters being preferred. As fatty acid polyol esters come Monobzw. Diesters of fatty acids with certain polyols. The fatty acids with the Polyols are esterified, preferably saturated or unsaturated fatty acids with 12 to 18 C atoms, for example lauric acid, myristic acid, palmitic acid or stearic acid, where preferably the technically obtained mixtures of the fatty acids are used, for example the acid mixtures derived from coconut, palm kernel or tallow fat. In particular acids or Mixtures of acids with 16 to 18 carbon atoms such as, for example, tallow fatty acid are used Suitable for esterification with the polyhydric alcohols. As polyols with the above mentioned fatty acids are esterified, come within the scope of the present invention sorbitol, Trimethylolpropane, neopentyl glycol, ethylene glycol, polyethylene glycols, glycerin and polyglycerols into consideration.

Preferred embodiments of the present invention provide that as a polyol, the Fatty acid (s) is esterified, glycerin is used. Accordingly, are according to the invention Detergent components are preferred which contain one or more fatty substances as ingredient c) the group of fatty alcohols and fatty acid glycerides. Particularly preferred Detergent components contain as component c) a fatty substance from the group of Fatty alcohols and fatty acid monoglycerides. Examples of such preferred fatty substances are glycerol monostearic acid esters and glycerol monopalmitic acid esters.

The particulate rinse aid according to the invention can preferably be used as ingredient d) further active substances and / or auxiliary substances from the groups of surfactants, bleaching agents, bleach activators, soil-release polymers, enzymes, silver preservatives, complexing agents, dyes and fragrances Amounts from 0 to 50% by weight, preferably from 2.5 to 45% by weight, particularly preferably from 5 up to 40% by weight and in particular from 10 to 30% by weight.

The use of the surfactants described above is particularly preferred, so that preferred particulate rinse aid are characterized in that they contain d) additionally surfactant (s), preferably nonionic surfactant (s), particularly preferably those from the Group of alkoxylated alcohols, in amounts from 5 to 47.5% by weight, preferably from 10 to 45 % By weight, particularly preferably from 15 to 42.5% by weight and in particular from 20 to 40% by weight, each based on the particulate rinse aid.

The other detergent ingredients used as component d) in the invention Rinse aid can be incorporated are described in detail below.

The particulate rinse aid according to the invention contains the ingredient e) Metal salts used according to the invention, the above statements regarding preferred species apply completely analogously. To avoid redundancies, therefore, the above mentioned formulas. Preferred particulate rinse aid contain one or several metal salts of ricinoleic acid and / or abietic acid, preferably zinc ricinoleate and / or zinc abietate, in particular zinc ricinoleate, in amounts of 0.5 to 60% by weight, preferably from 1 to 50% by weight, particularly preferably from 2.5 to 40% by weight and in particular from 5 to 30% by weight, based in each case on the particulate rinse aid.

a) 30 bis 70 Gew.-% Hüllsubstanz(en) mit einem Schmelzpunkt oberhalb von 50°C,

b) 0 bis 65 Gew.-% Fettstoff(en),

c) 0 bis 50 Gew.-% weiteren Wirk- und/oder Hilfsstoffe sowie

d) 0,1 bis 70 Gew.-% an Metallsalzen einer unverzweigten oder verzweigten, ungesättigten oder gesättigten, ein- oder mehrfach hydroxylierten Fettsäure mit mindestens 8 Kohlenstoffatomen und/oder einer Harzsäure mit Ausnahme der Alkalimetallsalze

auf ein oder mehrere Trägermaterialien aufbringt und die Mischung formgebend verarbeitet.Another object of the present invention is a method for producing particulate detergent components, which is characterized in that a melt from

a) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,

b) 0 to 65% by weight of fat (s),

c) 0 to 50% by weight of further active substances and / or auxiliaries and

d) 0.1 to 70% by weight of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts

applied to one or more carrier materials and the mixture processed shaping.

In this variant of the method, a melt is first produced, the further active and May contain auxiliaries. This is placed on a carrier material and mixed with it Base material processed to give shape.

In the production process mentioned for the rinse aid particles according to the invention Process variants preferred in which the meltable substance, 25 to 85% by weight, preferably 30 to 70 wt .-% and in particular 40 to 50 wt .-% of the melt.

The application of the melt to the carrier material can be done in all usual ways Mixing devices are carried out. The shaping processing step for the mixture made of melt and carrier material is also not subject to any process engineering Restrictions, so that the person skilled in the art can select from the methods familiar to him can. In tests by the applicant, methods have been found to be preferred in which the shaping processing by granulating, compacting, pelleting, extruding or Tableting takes place.

The method according to the invention comprises the application of melts from the ingredients a) to d) on carrier materials. In principle, the melt and carrier (s) can vary Amounts may be contained in the resulting rinse aid particles. Preferred methods are characterized in that a mixture of 5 to 50 wt .-%, preferably 10 to 45 wt .-%, particularly preferably 15 to 40% by weight and in particular 20 to 35% by weight of a melt from the ingredients a) to d) and 50 to 95 wt .-%, preferably 55 to 90 wt .-%, particularly preferably 60 to 85% by weight and in particular 65 to 80% by weight of carrier material (s) shaping is processed.

Regarding the ingredients used in the method according to the invention and the carrier material-based detergent components according to the invention are processed, the same applies as stated above.

The cleaning agent components according to the invention can also be formulated without a carrier material are so that they only consist of the ingredients a) to d). For the production Particulate detergent components according to the invention have been found in particular the preening, the pastilling and the scaling by means of chill rolls have proven their worth.

a) 30 bis 70 Gew.-% Hüllsubstanz(en) mit einem Schmelzpunkt oberhalb von 50°C,

b) 0 bis 65 Gew.-% Fettstoff(en),

c) 0 bis 50 Gew.-% weiteren Wirk- und/oder Hilfsstoffe sowie

d) 0,1 bis 70 Gew.-% an Metallsalzen einer unverzweigten oder verzweigten, ungesättigten oder gesättigten, ein- oder mehrfach hydroxylierten Fettsäure mit mindestens 8 Kohlenstoffatomen und/oder einer Harzsäure mit Ausnahme der Alkalimetallsalze

in einen Kaltgasstrom eindüst.Another object of the present invention is therefore, in a first embodiment, a process for producing prilled detergent components, in which a melt is made

a) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,

b) 0 to 65% by weight of fat (s),

c) 0 to 50% by weight of further active substances and / or auxiliaries and

d) 0.1 to 70% by weight of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts

injected into a cold gas stream.

The method according to the invention, which is briefly referred to as prilling, comprises the production granular body made of meltable substances, the melt consisting of the ingredients a) to d) the top of a tower is sprayed in a defined droplet size, solidifies in free fall and the prills at the bottom of the tower accumulate as granules.

In general, all gases can be used as the cold gas stream, the temperature of the gas is below the melting temperature of the melt. To avoid long falls, is often used with cooled gases, for example with frozen air or even with liquid nitrogen that is injected into the spray towers.

The grain size of the resulting prills can be varied by choosing the droplet size, particle sizes in the range from 0.5 to 2 mm, which are technically simple to implement, preferably around 1 mm.

a) 30 bis 70 Gew.-% Hüllsubstanz(en) mit einem Schmelzpunkt oberhalb von 50°C,

b) 0 bis 65 Gew.-% Fettstoff(en),

c) 0 bis 50 Gew.-% weiteren Wirk- und/oder Hilfsstoffe sowie

d) 0,1 bis 70 Gew.-% an Metallsalzen einer unverzweigten oder verzweigten, ungesättigten oder gesättigten, ein- oder mehrfach hydroxylierten Fettsäure mit mindestens 8 Kohlenstoffatomen und/oder einer Harzsäure mit Ausnahme der Alkalimetallsalze

auf gekühlte Pastillierteller dosiert.An alternative method of twisting is pastilling. A further embodiment of the present invention therefore provides a method for producing pelletized detergent components, in which a melt is removed

a) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,

b) 0 to 65% by weight of fat (s),

c) 0 to 50% by weight of further active substances and / or auxiliaries and

d) 0.1 to 70% by weight of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts

dosed on chilled pastilles.

Pastilling, which is sometimes referred to as pelleting, includes the dosage of Melt the ingredients a) through d) onto rotating, inclined plates that have a temperature have below the melting temperature of the melt and preferably below Be cooled to room temperature. Process variants can also be carried out here, where the pastilles are frozen. However, measures must be taken against this Condensing moisture can be taken.

The pastillation provides larger particles, the sizes between 2 and 10 mm, preferably between 3 and 6 mm.

a) 30 bis 70 Gew.-% Hüllsubstanz(en) mit einem Schmelzpunkt oberhalb von 50°C,

b) 0 bis 65 Gew.-% Fettstoff(en),

c) 0 bis 50 Gew.-% weiteren Wirk- und/oder Hilfsstoffe sowie

d) 0,1 bis 70 Gew.-% an Metallsalzen einer unverzweigten oder verzweigten, ungesättigten oder gesättigten, ein- oder mehrfach hydroxylierten Fettsäure mit mindestens 8 Kohlenstoffatomen und/oder einer Harzsäure mit Ausnahme der Alkalimetallsalze

auf eine Kühlwalze aufträgt oder aufsprüht, die erstarrte Schmelze abschabt und falls erforderlich zerkleinert.The use of cooling rollers is an even more cost-effective variant for producing particulate cleaning agent components of the composition mentioned from melts. Another object of the present invention is therefore a method for producing particulate detergent components, in which a melt is made

a) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,

b) 0 to 65% by weight of fat (s),

c) 0 to 50% by weight of further active substances and / or auxiliaries and

d) 0.1 to 70% by weight of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts

applied or sprayed onto a chill roll, scraped off the solidified melt and, if necessary, shredded.

The use of cooling rollers enables the desired setting to be made easily Particle size range, which in this method according to the invention is also below 1 mm, for example at 200 to 700 microns.

The rinse aid particles according to the invention can be given directly to the consumer be so that he also doses them to the detergent as needed. Because of this additional dosing step would be in addition to the fixed form of supply and the addition in the same dispenser minimizes the advantages over liquid rinse aid. It is preferred therefore, the rinse aid particles of the particulate machine dishwashing detergent according to the invention admix.

Another object of the present invention is therefore also a particulate automatic dishwashing detergent containing builders and optionally other ingredients the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, Polymers, dyes and fragrances containing a particulate rinse aid according to the invention Amounts from 0.5 to 30% by weight, preferably from 1 to 25% by weight and in particular from 5 to 15 wt .-%, each based on the total agent contains.

The ingredients of automatic dishwashing detergents are described below. Partly can these as active substances or carrier materials in the invention Rinse aid particles are included.

The main ingredients of machine dishwashing detergents are builders Detergents according to the invention for machine dishwashing can all be used builders usually used in detergents and cleaning agents, especially zeolites, silicates, carbonates, organic cobuilders and - if none There are ecological concerns about their use - including the phosphates. The below Builders mentioned are all as carrier materials for the inventive Rinse aid particles are suitable, as already explained above.

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 are. 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 .yH 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 in dissolving 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, compacting / 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 as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na ₂ O (1-n) K ₂ O Al ₂ O ₃ (2 - 2.5) SiO ₂ (3.5 - 5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. Among the large number of commercially available phosphates, the alkali metal phosphates are among particular preference for pentasodium or pentapotassium triphosphate (sodium or Potassium tripolyphosphate) in the detergent and cleaning agent industry.

Alkali metal phosphates is the general 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 a pH of 4.5 with sodium hydroxide solution 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 light 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 diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared 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 ) 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, for example, when 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 dewatering 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 differentiate 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] _n that crystallizes with 6 H ₂ O. -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; 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% strength 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 are exactly like sodium tripolyphosphate, potassium tripolyphosphate or Mixtures of these two can be used; also mixtures of sodium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and Sodium potassium tripolyphosphate can be used according to the invention.

As organic cobuilders in the dishwasher detergents according to the invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used become. These classes of substances are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function. For example, these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder 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 relative molecular mass from 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 made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. 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 2000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As particularly suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free Acids is generally 2,000 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 agents is 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.

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of acrylic acid as monomers and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts as monomers acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

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

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing effect Have effect.

Other suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, can be obtained. Preferred polyacetals are made from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as Obtain gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. They are preferably hydrolysis products with medium Molar masses in the range from 400 to 500000 g / mol. Here is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Both maltodextrins with a DE between 3 can be used and 20 and dry glucose syrups 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.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Farther glycerol disuccinates and glycerol trisuccinates are also preferred in this connection. Suitable amounts are 3 in zeolite and / or silicate formulations up to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least 4 carbon atoms and at least one hydroxyl group and a maximum of two Acid groups included.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly special Meaning as a cobuilder. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in Question. They are preferably in the form of the neutral sodium salts, e.g. as Hexasodium salt of EDTMP or as hepta and octa sodium salt of DTPMP. As Builder from the phosphonate class is preferably HEDP. The Aminoalkanephosphonates also have a strong ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, it may be preferred Aminoalkanephosphonate, especially DTPMP to use, or mixtures of the to use the named phosphonates.

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

In addition to the builders, substances from the groups of surfactants (see above) include Bleach, bleach activators, enzymes, polymers, colors and fragrances important ingredients of detergents. Important representatives from the above Substance classes are described below.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as 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-phthalimidanoic acid paprooxyaprooxyacroperaproic acid , o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1,4- diacid, N, N-terephthaloyldi (6-aminopercapronic acid) can be used.

As a bleaching agent in the cleaning agents according to the invention for machine dishwashing substances that release chlorine or bromine can also be used. Among the appropriate ones Chlorine or bromine-releasing materials come, for example, from heterocyclic N-bromine 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 in Consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleaches mentioned can also be used entirely to achieve "post-bleaching" in the rinse aid or partly via the rinse aid particles according to the invention into the inventive machine dishwashing detergent.

Bleach activators that support the action of the bleach have already been described above possible ingredient of the rinse aid particles mentioned. Known bleach activators are Compounds that contain one or more N- or O-acyl groups, such as substances from the Class of anhydrides, esters, imides and acylated imidazoles or oximes. examples are Tetraacetylethylenediamine TAED, Tetraacetylmethylenediamine TAMD and Tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used. Are suitable Substances containing O- and / or N-acyl groups of the number of carbon atoms mentioned and / or if appropriate carry substituted benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (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) as well as acetylated sorbitol and mannitol respectively their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetylfructose, 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 also be used be used.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts are incorporated into the rinse aid particles. With these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as 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 as well as Co, Fe, Cu and Ru-amine complexes can be used as bleaching catalysts.

Bleach activators from the group of multi-acylated alkylenediamines are preferred, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in Quantities up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6 wt .-% based on the total agent used.

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

In the cleaning agents according to the invention, the enzymes in particular come from Classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, Amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases help remove soiling such as protein, fat or starch Stains on. Oxidoreductases can also be used for bleaching. Particularly good are suitable from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetic engineering modified variants obtained enzymatic active ingredients. 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 lipolytically active enzymes or protease, lipase or lipolytically active enzymes, in particular, however, protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic acting enzymes are the well-known cutinases. Peroxidases or oxidases have also become proved suitable in some cases. Suitable amylases include in particular alpha amylases, Iso-amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or embedded in enveloping substances around them protect 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 wt .-% be.

Dyes and fragrances can be added to the automatic dishwashing detergents according to the invention to improve the aesthetic impression of the resulting products and the Consumers in addition to performance a visually and sensory "typical and distinctive" To provide product. Individual as perfume oils or fragrances Fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde type, Ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the type Esters are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, Dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, Citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and bourgeonal, to the ketones e.g. the Jonone, α-Isomethylionon and Methylcedrylketon, to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol The hydrocarbons mainly include the terpenes such as limonene and pinene. Prefers however, mixtures of different odoriferous substances are used, which together form an appealing Generate fragrance. Such perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, Rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile 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 fragrances can be incorporated directly into the cleaning agents according to the invention But it can also be advantageous to apply the fragrances to carriers that increase the adhesion of the Increase perfumes on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles. Such carrier materials have, for example Cyclodextrins have proven their worth, with the cyclodextrin-perfume complexes additionally with others Auxiliaries can be coated. Also an incorporation of the fragrances into the Rinse aid particles according to the invention is possible and leads to a scent impression when opened the machine (see above).

In order to improve the aesthetic impression of the agents produced according to the invention, it can (or parts thereof) can be colored with suitable dyes. Preferred dyes whose Selection presents no difficulty for the expert, has a high storage stability and Insensitivity to the other ingredients of the agents and to light and none pronounced substantivity towards the substrates to be treated with the agents such as glass, Ceramics or plastic dishes so as not to stain them.

The cleaning agents according to the invention can protect the dishes or the machine Corrosion inhibitors contain, especially silver protection in the field of mechanical Dishwashing have a special meaning. The known substances can be used the state of the art. In general, silver protection agents can be selected from the Group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Alkylaminotriazoles and the transition metal salts or complexes are used. Especially benzotriazole and / or alkylaminotriazole are preferred. One finds in In addition, detergent formulations often contain active chlorine agents that corrode the Can significantly reduce the silver surface. Chlorine-free cleaners are special Organic and redox-active compounds containing oxygen and nitrogen, such as divalent and trivalent Phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic Compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. The transition metal salts selected from the group of manganese are preferred and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or Manganese and manganese sulfate. Zinc compounds can also be used to prevent the Corrosion can be used on the wash ware.

The composition of the rinse aid particles according to the invention is designed such that they are not in the main wash cycle (and also in optional pre-wash cycles) or only in dissolve to a minor extent. This ensures that the active substances only in Rinse aid are released and have their effect here. In addition to this chemical Depending on the type of dishwasher, assembly is a physical assembly required so that the rinse aid particles do not drain out when the water is changed in the machine and are therefore no longer available for the rinse aid. Common household Dishwashers contain before the drain pump, which the water or Pumps cleaning solution out of the machine after each cleaning cycle, one Sieve insert, which is intended to prevent the pump from becoming blocked by dirt residues. Will be from If heavily soiled dishes are washed by consumers, this strainer must be cleaned regularly become, which is easily possible due to the easy accessibility and removability. The rinse aid particles according to the invention are now of a size and shape preferably designed so that you can use the dishwasher after the Cleaning cycle, i.e. after exposure to movement in the machine and the cleaning solution, not happen. This ensures that rinse aid particles are present in the rinse aid the dishwasher, which under the influence of the warmer water Release active substance (s) and bring the desired rinse aid effect. As part of the Preferred particulate machine dishwashing detergents are thereby characterized in that the particulate rinse aid has particle sizes between 1 and 40 mm, preferably between 1.5 and 30 mm and in particular between 2 and 20 mm.

In the dishwashing detergents according to the invention, the rinse aid particles with the above protruding sizes from the matrix of the other particulate ingredients that other particles can also have sizes that lie in the range mentioned, so that a total of a detergent is formulated from large detergent and There are rinse aid particles. Especially when the rinse aid particles according to the invention be colored, e.g. have a red, blue, green or yellow color, it is for the appearance of the product, i.e. of the entire cleaning agent is advantageous if the Rinse aid particles are visibly larger than the matrix of the particles of the other ingredients in the Detergent. Here are particulate machine dishwashing detergents according to the invention preferred that (without taking into account the rinse aid particles) particle sizes between 100 and 3000 µm, preferably between 300 and 2500 µm and in particular between 400 and 2000 µm exhibit.

The optical appeal of such compositions can, in addition to the coloring of the rinse aid particles also by contrasting coloring of the powder matrix or by the shape of the rinse aid particles increase. Because the manufacture of rinse aid particles is technically uncomplicated Procedures can be used, it is easily possible to use these in the to offer a wide variety of shapes. In addition to the particle shape, which is almost spherical has, for example, cylindrical or cube-shaped particles can be produced and used. Other geometric shapes can also be realized. Special product designs can contain star-shaped rinse aid particles, for example. Also slices or Forms that are used as the base of plants and animal bodies, for example tree, flower, blossom, sheep, Show fish etc. can be easily produced. Interesting visual incentives can be found on these Wise also create that the rinse aid particles in the form of a stylized glass made to visually underline the rinse aid effect in the product. Are the imagination there are no limits.

If the cleaning agents according to the invention are formulated as a powder mixture, especially 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 differ in two successive cleaning cycles be as the consumer does not always necessarily have the same amount of detergent and rinse aid particles dosed. If desired, technically always the same amount per cleaning cycle to use, this can be done using the packaging of the invention which is familiar to the person skilled in the art Means can be realized in bags made of water-soluble film. Also particulate mechanical Dishwashing detergent, in which a dosing unit in a bag made of water-soluble film is welded, are the subject of the present invention.

As a result, the consumer only has one bag, for example a detergent powder and contains several optically prominent rinse aid particles in the dispenser of his Put in the dishwasher. This embodiment of the present invention is therefore a visually appealing alternative to conventional detergent tablets.

The cleaning agents according to the invention can be produced in a manner known per se. A method of producing powdered machine dishwashing detergent with rinse aid effect, in which a powdered machine dishwashing agent known per se is mixed with rinse aid particles according to the invention, is therefore a further subject of the present invention.
The desired retention of the rinse aid particles in the machine described above, even when changing water, can be achieved in addition to the above-mentioned enlargement of the rinse aid particles by reducing the holes in the sieve insert. In this way, machine dishwashing detergents can be formulated which have a uniform mean particle size which is smaller than, for example, 4 to 12 mm. For this purpose, a sieve insert is added to the product according to the invention, in which the rinse aid particles also have smaller particle sizes, which replaces or covers the insert located in the machine. Another object of the present invention is therefore a kit-of-parts, which comprises a powdered dishwasher detergent according to the invention and a sieve insert for household dishwashers.

As already mentioned, the combination of agent and sieve insert according to the invention allows Formulation of agents in which the rinse aid particles also have smaller particle sizes exhibit. Kits-of-parts according to the invention, in which the particle sizes of the machine Dishwashing detergent (taking into account the rinse aid particles) in the range from 400 to 2500 µm, preferably from 500 to 1600 µm and in particular from 600 to 1200 µm, are included prefers.

In order to prevent clogging of the enclosed sieve insert due to dirt residues, the Mesh size or hole size should not be chosen too small. Here are kits of parts according to the invention preferred, in which the mesh size or hole size of the sieve insert 1 to 4 mm and the rinse aid particles are larger than this mesh size or hole size of the Screen insert.

The kit of parts according to the invention is not restricted to the specific shape of the sieve insert, where it replaces or covers the insert in the machine. It is According to the invention, it is also possible and preferred to include a sieve insert in the kit of parts has the shape of a basket, which in a known manner in the dishwasher - for example on the cutlery basket - can be hung. This way it replaces a sieve insert designed in this way the dosing chamber, i.e. the consumer doses that Machine dishwashing detergent according to the invention directly in this sieve insert, which in the cleaning and Rinse aid acts in the manner described above.

The advantages according to the invention may also apply to the compact form be used. Another object of the present invention is therefore a Detergent tablets for machine dishwashing, containing builders and optionally further ingredients of cleaning agents, one or more metal salts unbranched or branched, unsaturated or saturated, single or multiple hydroxylated Fatty acid with at least 8 carbon atoms and / or a resin acid other than Alkali metal salts in amounts of 0.5 to 60% by weight, preferably 1 to 50% by weight, particularly preferably from 2.5 to 40% by weight and in particular from 5 to 30% by weight, in each case based on the weight of the molded body.

Here too, reference can be made to the above information with regard to preferred embodiments to get expelled. As already mentioned, the introduction of those to be used according to the invention is necessary Metal salts in the rinse aid are particularly preferred, so preferred Detergent tablets are characterized in that they contain the metal salts release-delayed form included.

Not only is a release delay particularly preferred, but a controlled one Release that is not due to slower solubility but due to external circumstances controlled release. The rinse aid particles described above can also be used as Shaped body phase can be formulated and also offer the possibility of in shaped bodies Temperature-controlled release of the metal salts to be used according to the invention.

a) 0 bis 65 Gew.-% eines oder mehrerer Trägermaterialien,

b) 30 bis 70 Gew.-% Hüllsubstanz(en) mit einem Schmelzpunkt oberhalb von 50°C,

c) 0 bis 65 Gew.-% Fettstoff(e),

d) 0 bis 50 Gew.-% weiterer Wirk- und/oder Hilfsstoffe sowie

e) 0,1 bis 70 Gew.-% an Metallsalzen einer unverzweigten oder verzweigten, ungesättigten oder gesättigten, ein- oder mehrfach hydroxylierten Fettsäure mit mindestens 8 Kohlenstoffatomen und/oder einer Harzsäure mit Ausnahme der Alkalimetallsalze

besteht.The present invention therefore furthermore relates to multiphase detergent tablets for machine dishwashing, containing builders and optionally further detergent ingredients in which at least one phase consists of

a) 0 to 65% by weight of one or more carrier materials,

b) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,

c) 0 to 65% by weight of fat (s),

d) 0 to 50% by weight of further active substances and / or auxiliaries and

e) 0.1 to 70 wt .-% of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts

consists.

Are completely analogous to the above explanations for the particulate rinse aid same embodiments (amount, type and packaging of the ingredients, etc.) also in the moldings of the invention preferred.

In the context of the present invention, the individual phases of the shaped body can have different spatial shapes. The simplest possible implementation is in two- or multi-layer tablets, with each layer of the shaped body representing a phase. However, it is also possible according to the invention to produce multiphase molded articles in which individual phases have the form of inclusions in another phase (s). In addition to so-called "ring core tablets", coated tablets or combinations of the above-mentioned embodiments are possible, for example. Examples of multi-phase moldings can be found in the illustrations in EP-A-0 055 100 (Jeyes), which describes toilet cleaning blocks. The most widespread spatial form of multi-phase tablets is the two- or multi-layer tablet. In the context of the present invention, it is therefore preferred that the phases of the shaped body have the shape of layers and the shaped body is 2-, 3- or 4-phase.

The moldings according to the invention can take on any geometric shape, wherein in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, hexagonal and octagonal prismatic as well rhombohedral shapes are preferred. Also completely irregular bases such as arrow or Animal forms, trees, clouds, etc. can be realized. Assign the inventive Shaped body corners and edges, they are preferably rounded. As an additional optical differentiation is an embodiment with rounded corners and beveled ("chamfered") edges preferred.

Instead of the layer structure, it is also possible to produce moldings which are the ones according to the invention Include detergent component in the form of other phases. It has proven itself here To produce base moldings which have one or more cavity (s) and the melt from the ingredients a) to d) of the detergent component according to the invention into the cavity fill in and freeze there. This manufacturing process results in preferred multi-phase detergent tablets, which consist of a base tablet, which has a cavity, and consist of at least partially contained in the cavity.

The cavity in the pressed part of such shaped bodies according to the invention can have any shape exhibit. It can cut through the molded part, i.e. an opening on different sides, For example, have on the top and bottom of the molded body, but it can not be one be through the entire molded body cavity, the opening of only one Shaped body side is visible. The shape of the cavity can also be freely selected within wide limits become. For reasons of process economy, there are continuous holes in them Openings lie on opposite surfaces of the molded body, and troughs with a Proven opening on one side of the molded body. In preferred washing and Detergent tablets have the cavity in the form of a through hole, the Openings are located on two opposing shaped body surfaces. The shape of one through hole can be chosen freely, molded bodies are preferred in which the through hole circular, elliptical, triangular, rectangular, square, pentagonal, has hexagonal, heptagonal or octagonal horizontal sections. Completely irregular too Hole shapes such as arrow or animal shapes, trees, clouds, etc. can be realized. As well as in the case of the shaped bodies, in the case of angular holes, those with rounded corners and Edges or with rounded corners and chamfered edges preferred.

The geometric implementation forms mentioned above can be combined with one another as desired combine. Shaped bodies with a rectangular or square base and circular holes are produced as well as round shaped bodies with octagonal holes, whereby there are no limits to the variety of possible combinations. Because of Process economics and aesthetic consumer perception are molded articles with holes particularly preferred in which the shaped body base area and the hole cross section are the same have geometric shape, for example shaped bodies with a square base area and central incorporated square hole. Ring-shaped bodies, i.e. circular shaped body with a circular hole.

If the above Principle of the hole open on two opposite sides of the molded body on one Opening is reduced, mold bodies are obtained. Washing and Detergent tablets in which the cavity has the shape of a trough are also prefers. As with the "hole moldings", the moldings according to the invention can also be used this embodiment assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, five-, seven- and octagonal-prismatic and rhombohedral shapes are preferred. Also completely irregular base areas such as arrow or animal shapes, trees, clouds etc. can be realized. If the molded body has corners and edges, these are preferably rounded. As an additional optical differentiation, an embodiment with rounded corners and chamfered ("chamfered") edges preferred.

The shape of the trough can also be chosen freely, preference being given to moldings in which at least one trough a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, hexagonal and octagonal prismatic as well rhombohedral shape can take. Completely irregular trough shapes such as arrow or Animal forms, trees, clouds, etc. can be realized. As with the shaped bodies Troughs with rounded corners and edges or with rounded corners and chamfered edges prefers.

a) 0 bis 10 Gew.-%, vorzugsweise 0 bis 7,5 und insbesondere 0 bis 5 Gew.-% eines oder mehrerer Trägermaterialien,

b) 30 bis 70 Gew.-%, vorzugsweise 35 bis 65 Gew.-% und insbesondere 40 bis 60 Gew.-% Hüllsubstanz(en) mit einem Schmelzpunkt oberhalb von 50°C,

c) 0 bis 65 Gew.-%, vorzugsweise 10 bis 60 Gew.-% und insbesondere 20 bis 50 Gew.-% Fettstoff(e),

d) 0 bis 50 Gew.-%, vorzugsweise 5 bis 45 Gew.-% und insbesondere 10 bis 40 Gew.-% weiterer Wirk- und/oder Hilfsstoffe sowie

e) 0,1 bis 70 Gew.-%, vorzugsweise 1 bis 50 Gew.-% und insbesondere 5 bis 40 Gew.-% Metallsalzen einer unverzweigten oder verzweigten, ungesättigten oder gesättigten, einoder mehrfach hydroxylierten Fettsäure mit mindestens 8 Kohlenstoffatomen und/oder einer Harzsäure mit Ausnahme der Alkalimetallsalze

besteht.In the case described above, the part at least partially contained in the cavity consists solely of the ingredients a) to d) of the detergent components. However, it is also possible to introduce detergent components based on carrier material into the cavity (s). For reasons of process economy, however, multiphase detergent tablets are preferred in which the part contained in the cavity is made of

a) 0 to 10% by weight, preferably 0 to 7.5 and in particular 0 to 5% by weight of one or more carrier materials,

b) 30 to 70% by weight, preferably 35 to 65% by weight and in particular 40 to 60% by weight of coating substance (s) with a melting point above 50 ° C.,

c) 0 to 65% by weight, preferably 10 to 60% by weight and in particular 20 to 50% by weight of fat (s),

d) 0 to 50% by weight, preferably 5 to 45% by weight and in particular 10 to 40% by weight of further active substances and / or auxiliaries and

e) 0.1 to 70% by weight, preferably 1 to 50% by weight and in particular 5 to 40% by weight, of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid other than the alkali metal salts

consists.

The recipes described above can vary depending on the content of carriers and amounts melted on the individual ingredients and entered as a melt into the cavity where they solidify to the part contained in the cavity. But it is also possible to do that or the metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydric fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts in a tablettable premix and from it to press a smaller tablet, which then forms the "core" in a basic tablet with a cavity is transferred. There the press core can either adhere due to its geometry or with Adhesion promoters are stuck.

Alternatively, the prefabricated core can be fed to a tablet press and there with another Particulate premix can be pressed into a tablet Premix metering is carried out so that the core has already metered it into the die Premix is added, or that the premix is placed on the core placed in the die is filled. In the first case you get a so-called point tablet, the core of which is on the top is visible, while the second approach corresponds to tablets rotated by 180 ° supplies. If one doses premix into the matrix before and after adding the core, the core becomes completely enclosed by the resulting tablet and you get so-called Kernmantel tablets.

Corresponding processes for the production of so-called point tablets and Core coated tablets are known from the pharmaceutical industry.

The size of the trough or through hole compared to the entire molded body depends on the intended use of the molded body. Depending on how much further active substance, the remaining hollow volume should be filled and whether a smaller one or larger amount of detergent component should be included, the size of the Cavity vary. Regardless of the intended use, washing and Preferred detergent tablets, in which the volume ratio of the pressed part ("Base molding") for detergent component 2: 1 to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1.

In addition to the volume ratio mentioned, a mass ratio of the two parts can also are specified, the two values relating to the densities of the base molding and the Correlate detergent components with each other. Regardless of the density of each Parts of detergent tablets according to the invention are preferred in which the Weight ratio of base molding to detergent component 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1 is.

Analogous statements can also be made for the surfaces, in each case of the base molding or are visible from the detergent component. Here are washing or Preferred detergent tablets, in which the outwardly visible surface of the Detergent component 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15 % and in particular 4 to 10% of the total surface of the molded body

The detergent component and the base molding are preferably optical distinctively colored. In addition to the optical differentiation, application technology Advantages achieved through different solubilities of the different shaped body regions become. Detergent tablets, in which the detergent component dissolves faster than the base molding, are preferred according to the invention. By incorporation Certain components can, on the one hand, specifically target the solubility of the detergent component accelerated, on the other hand, the release of certain ingredients from the Detergent components lead to advantages in the washing or cleaning process.

Of course, detergent tablets according to the invention are also molded preferred, in which the detergent component dissolves later in the washing program than that Basic tablet. Performance benefits from this delayed release can be seen, for example thereby achieve that with the help of a slower soluble detergent component Active substance (s) are only released in later rinses. For example, at machine dishwashing achieved by detergent components that dissolve more slowly that additional active substance (s) is / are available in the rinse aid cycle. By additional substances such as nonionic surfactants, acidifying agents, soil release polymers etc. the rinse aid results can be improved in this way. There is also an incorporation of perfume possible without any problems; due to its delayed release, it can often occur in dishwashers "Lye smell" occurring when opening the machine can be eliminated. The ingredients Acidifiers, soil release polymers, etc. are based on the inventive ones Detergent components then sourced ingredients d).

In preferred embodiments of the present invention, the base molding has a high specific weight. Detergent tablets, which are characterized in that the base tablet has a density above 1000 kgdm ^-3 , preferably above 1025 kgdm ^-3 , particularly preferably above 1050 kgdm ^-3 and in particular above 1100 kgdm ^-3 , are according to the invention prefers.

In order to facilitate the disintegration of highly compressed moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into them in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.

These substances, which are also called "explosives" due to their effect, enlarge their volume in the event of water ingress, on the one hand increasing their own volume (swelling), on the other hand, a pressure can be generated via the release of gases, which the Tablet breaks into smaller particles. Well-known disintegration aids are for example carbonate / citric acid systems, with other organic acids can be used. Swelling disintegration aids are, for example, synthetic Polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified natural products such as Cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, in each case based on the weight of the molded article. Contains only the basic molding disintegration aid, so The information given relates only to the weight of the base molding. In the Incorporation of disintegration aids into the inventive Detergent components count those as ingredient d).

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight .-% contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be compressed. Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO 98/40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above-mentioned coarser disintegration aids based on cellulose which are described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from the company Rettenmaier.

As a further disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is made by partial Hydrolysis of celluloses obtained under conditions that only the amorphous areas (approx. Attack 30% of the total cellulose mass) of the celluloses and completely dissolve that leave crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the The microfine celluloses produced by the hydrolysis provide the microcrystalline celluloses, which have primary particle sizes of approx. 5 µm and, for example, granules with a average particle size of 200 microns are compactible.

Contain preferred detergent tablets within the scope of the present invention additionally a disintegration aid, preferably a disintegration aid Cellulose base, preferably in granular, cogranulated or compacted form, in quantities from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, each based on the weight of the molded body.

The detergent tablets according to the invention can moreover both in Basic molded body as well as a gas-developing shower system in the detergent component contain. The gas evolving shower system can consist of a single substance, which at Contact with water releases a gas. Among these connections is particularly that To name magnesium peroxide, which releases oxygen on contact with water. Usually however, the gas-releasing bubble system itself consists of at least two components, that react with each other to form gas. While here a multitude of systems think and is executable, which release nitrogen, oxygen or hydrogen, for example Bubble system used in the detergent tablets according to the invention Let you choose based on both economic and ecological considerations. Preferred shower systems consist of alkali metal carbonate and / or bicarbonate as well an acidifying agent suitable from the alkali metal salts in aqueous solution Release carbon dioxide.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are out Cost reasons clearly preferred over the other salts. Needless to say the pure alkali metal carbonates or bicarbonates concerned are not used; rather, mixtures of different carbonates and hydrogen carbonates can be formed washing technology be preferred.

In preferred shaped detergent bodies, 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% an acidifying agent, based in each case on the entire molded body.

As acidifying agents that release carbon dioxide from the alkali salts in aqueous solution for example boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, organic are preferred Acidifier used, with citric acid being a particularly preferred Acidifier is. However, the other solid mono- and oligounds can also be used in particular Polycarboxylic acids. From this group tartaric acid, succinic acid, Malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. organic Sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as Acidifying agent is also preferably used in the context of the present invention Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), Glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

In the context of the present invention, preference is given to detergent tablets in which Acidifying agent in the shower system a substance from the group of organic di-, tri- and Oligocarboxylic acids or mixtures of these are used.

The particulate detergents and / or detergent tablets can - like the detergent components per se - be packaged after manufacture, the use of certain packaging systems having proven particularly useful. A further aspect of the present invention is a combination of (a) particulate cleaning agent (s) according to the invention and / or (a) detergent tablet (s) according to the invention and a packaging system containing the cleaning agent and / or the detergent tablet (s), wherein the packaging system has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

The packaging system of the combination of detergent component and / or detergent and / or detergent tablets (s) and packaging system according to the invention has a moisture vapor permeability rate of 0.1 g / m ² / day to less than 20 g / m ² / day, if that Packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. The specified temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined according to further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested. The moisture vapor permeability rate can be determined from the surface of the container which is closed with the material to be tested (permeation surface), the weight gain of the calcium chloride and the exposure time FDDR = 24 · 10000 A , x y [ G / m 2 / 24 H ] calculate, where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium humidity, often referred to as "relative humidity", is 85% at 23 ° C. when measuring the moisture vapor transmission rate in the context of the present invention. The absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ³ . For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor; at a temperature of 11 ° there is already saturation with 10 g of water vapor. The relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air contains 17 ° 12 g / m ³ water vapor, then the relative humidity = (12 / 14.4) 100 = 83%. If you cool this air, then the saturation (100% r.L.) is reached at the so-called dew point (in the example: 14 °), ie, if it cools further, a precipitate is formed in the form of fog (dew). Hygrometers and psychrometers are used for the quantitative determination of moisture.

The relative equilibrium humidity of 85% at 23 ° C can be found, for example, in Laboratory chambers with humidity control to +/- 2% RH depending on the device type. adjust exactly. Also over saturated solutions of certain salts form in closed systems given temperature constant and well-defined relative humidity levels on the Phase equilibrium between the partial pressure of water, saturated solution and soil based.

The combinations according to the invention can of course in turn Secondary packaging, such as cardboard boxes or trays, are packed, with the Secondary packaging no further requirements have to be made. The Secondary packaging is therefore possible, but not necessary.

Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m ² / day to less than 15 g / m ² / day.

The packaging system of the combination according to the invention encloses depending on Embodiment of the invention a certain amount of detergent component according to the invention, a certain amount of a particulate detergent composition or one or more detergent tablets. It is there preferred according to the invention, either to design a shaped body such that it has a Application unit of the detergent and cleaning agent includes, and this molding individually pack, or pack the number of moldings in one packaging unit, the total includes an application unit. With a nominal dosage of 80 g of detergent and cleaning agent it is therefore possible according to the invention to use an 80 g laundry detergent and cleaning product tablet to produce and pack individually, but it is also possible according to the invention, two 40 g each to pack heavy detergent tablets into a packaging in order to form a combination to arrive. This principle can be taken for granted expand, so that combinations according to the invention also three, four, five or even more washing and Detergent tablets can contain in a packaging unit. Of course Two or more molded articles can have different compositions in one package exhibit. In this way it is possible to spatially separate certain components separate, for example to avoid stability problems.

The packaging system of the combination according to the invention can be of the most varied Materials exist and take on any external shape. For economic reasons and however, packaging systems are preferred for reasons of easier processing which the packaging material is lightweight, easy to process and inexpensive is. In combinations preferred according to the invention, the packaging system consists of a Sack or bag made of single-layer or laminated paper and / or plastic film.

The detergent tablets can be unsorted, i.e. as a loose fill, in a bag can be filled from the materials mentioned. But it is for aesthetic reasons and preferred for sorting the combinations in secondary packaging, the washing and Fill detergent tablets individually or in groups in sacks or bags. For individual application units of the detergent tablets, which are in one Sack or bag, the term "flow pack" has become common in technology. Such "Flow packs" can then - again preferably sorted - optionally in outer packaging be packed, which underlines the compact form of the molded body.

The sacks or bags made of single-layer or laminated paper or plastic film, which are preferably used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam, which is sealed by heat (hot fusion), adhesives or adhesive tapes become. Single-layer bag or sack materials are the known papers, which can optionally be impregnated, and plastic films, which can optionally be co-extruded. Plastic films that can be used as a packaging system in the context of the present invention are specified , for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193 . Figure 111 shown there also provides information on the water vapor permeability of the materials mentioned.

Combinations particularly preferred in the context of the present invention contain as Packaging system with a sack or bag made of single-layer or laminated plastic film a thickness of 10 to 200 microns, preferably from 20 to 100 microns and in particular from 25 to 50 microns.

Although it is possible, wax-coated in addition to the films or papers mentioned Papers in the form of cardboard packaging systems for washing and Using detergent tablets, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax-coated paper. The term "In the context of the present invention, the packaging system always characterizes the Primary packaging of the detergent component, detergent composition or Molded articles, i.e. the packaging that is directly on the inside with the Detergent component, detergent composition or molded body surface in Contact is. There are no requirements for an optional secondary packaging that all common materials and systems can be used here.

As already mentioned above, the detergent components contain Detergent compositions or detergent tablets of Combination according to the invention further ingredients of depending on their intended use Detergents and cleaning agents in varying amounts. Regardless of the purpose of the According to the invention, it is preferred that the agent or agents Detergent tablets have a relative equilibrium moisture content of less than 30% at 35 ° C.

The relative equilibrium moisture content of the detergent or detergent tablets can be determined using common methods, whereby within the scope of the present The following procedure was chosen: A water-impermeable 1 liter container with a lid, which has a closable opening for the introduction of samples has been filled with a total of 300 g of detergent tablets and 24 hours at kept constant 23 ° C to keep the temperature of the vessel and substance constant guarantee. The water vapor pressure in the space above the moldings can then be measured with a Hygrometer (Hygrotest 6100, Testoterm Ltd., England) can be determined. The water vapor pressure is now measured every 10 minutes until two successive values show no deviation (Equilibrium moisture). The above Hygrometer allows a direct display of the values in% relative humidity.

Embodiments of the combination according to the invention are also preferred, in which the Packaging system is designed to be resealable. Combinations where the Packaging system has a microperforation can be preferred according to the invention realize.

As mentioned above, detergent components, detergent compositions or detergent tablets for automatic dishwashing produce by the methods of the invention. Accordingly, is a cleaning process for cleaning dishes in a dishwasher, characterized in that one or several particulate cleaning agents according to the invention and / or one or several detergent tablets according to the invention the metering chamber of the Insert dishwasher and run a washing program, in the course of which the Dosing chamber opens and the cleaning agent (s) and / or the molding (s) be resolved, another object of the present invention.

The metering chamber can also be dispensed with in the cleaning process according to the invention and the detergent components or detergent compositions according to the invention or the molded article (s) according to the invention, for example in the Insert the cutlery basket. It goes without saying that a dosing aid is also used here, For example, a basket that is placed in the washroom is no problem. Accordingly, a cleaning process for cleaning dishes in one Dishwasher, characterized in that one or more (s) according to the invention Particulate detergent and / or one or more washing or inventive Detergent tablets with or without dosing aid in the dishwasher's wash cabinet inserted and runs a rinse program, in the course of which the cleaning agent or cleaning agents and / or the shaped body or bodies are dissolved, a further subject of the present Invention.

The metal salts described above can also be used for a separate application Effect are introduced into the dishwasher, with specially designed dosing Get involved. Such "deodorant hangers" are commercially available for fragrances. The Corresponding articles can also be used to apply the metal salts, the Metal salts either alone or in a mixture with other substances, in particular perfume the articles may exist. Another object of the present invention is an article for hanging in the dishwasher, comprising a container which has at least one Has side made of a permeable material and a composition by the permeable material can escape, the composition of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid at least 8 carbon atoms and / or a resin acid other than the alkali metal salts contains.

Also in this embodiment, certain metal salts are preferred, so preferred articles characterized in that the composition one or more metal salts of Ricinoleic acid and / or abietic acid, preferably zinc ricinoleate and / or zinc abietate, contains in particular zinc ricinoleate.

The articles according to the invention are produced in preferred embodiments so that a Thermoformed film that forms an open hollow shape. After filling with one The composition, which contains the metal salts and possibly other ingredients, is the Hollow mold then closed with another film. It is preferred here for the film To choose deep-drawn part impermeable to the composition contained later in the article, while the sealing film is permeable to the metal salt-containing under conditions of use Composition is. To loss of active substance during storage and in To avoid display shelves, the permeable film can be covered with an impermeable, peelable Foil, for example aluminum foil (so-called "peel push foil") are closed. Here Articles according to the invention are preferred in which only one side wall of the container is made of Permeable material exists and this side closed with removable, non-permeable film is.

The containers of the articles according to the invention can also be designed in multi-chamber form, so that the consumer by pulling the "peel-push film" from the individual chambers Active intensity can determine itself by removing the film from one or more chambers away.

Claims (20)

Use of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts, in machine Dishwashing detergents. Use of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts, in the rinse aid at machine dishwashing. Use according to one of claims 1 or 2, characterized in that one or more metal salts of ricinoleic acid and / or abietic acid, preferably zinc ricinoleate and / or zinc abietate, in particular zinc ricinoleate, are used. Rinse aid for automatic dishwashing, containing metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid other than the Alkali metal salts. Rinse aid according to claim 4, characterized in that it contains the metal salt (s) in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular 0.5 to 10% by weight. , each based on the rinse aid. Rinse aid according to one of claims 4 or 5, characterized in that it contains surfactant (s), preferably nonionic surfactant (s) and in particular nonionic surfactant (s) from the group of the alkoxylated alcohols, in amounts of 0, 1 to 60 wt .-%, preferably from 0.5 to 50 wt .-%, particularly preferably from 1 to 40 wt .-%, and in particular from 2 to 30 wt .-%, each based on the rinse aid. Rinse aid according to one of claims 4 to 6, characterized in that it is non-aqueous solvent (s), preferably ethanol, n-propanol, i-propanol, 1-butanol, 2-butanol, glycol, propanediol, butanediol, glycerol, diglycol, propyl diglycol , Butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or methoxy, or, ethyl ether, or 1-Butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Particulate rinse aid for machine dishwashing, characterized in that it a) 0 to 65% by weight of one or more carrier materials, b) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C., c) 0 to 65% by weight of fat (s), d) 0 to 50% by weight of further active substances and / or auxiliaries and e) 0.1 to 70 wt .-% of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts contains. Particulate rinse aid according to claim 8, characterized in that it contains one or more metal salts of ricinoleic acid and / or abietic acid, preferably zinc ricinoleate and / or zinc abietate, in particular zinc ricinoleate, in amounts of 0.5 to 60% by weight, preferably 1 to Contains 50% by weight, particularly preferably from 2.5 to 40% by weight and in particular from 5 to 30% by weight, in each case based on the particulate rinse aid. Particulate rinse aid according to one of claims 8 or 9, characterized in that it contains, as ingredient b), one or more substances with a melting range between 50 and 100 ° C, preferably between 52.5 and 80 ° C and in particular between 55 and 75 ° C , contains, wherein paraffin waxes with a melting range of 50 ° C to 65 ° C and / or substances from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are preferred coating substances. Particulate rinse aid according to one of claims 8 to 10, characterized in that it additionally contains surfactant (s), preferably nonionic surfactant (s), particularly preferably those from the group of the alkoxylated alcohols, in amounts of 5 to 47.5% by weight, preferably from 10 to 45% by weight, particularly preferably from 15 to 42.5% by weight and in particular from 20 to 40% by weight, based in each case on the particulate rinse aid. Detergent tablets for machine dishwashing, containing builders and optionally further ingredients of detergents, characterized in that they contain one or more metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts in amounts of 0.5 to 60% by weight, preferably 1 to 50% by weight, particularly preferably 2.5 to 40% by weight and in particular 5 to 30% by weight, in each case based on the molded body weight. Shaped detergent body according to claim 12, characterized in that it contains the metal salts in a delayed release form. Multi-phase detergent tablets for automatic dishwashing, containing builders and optionally further detergent ingredients, characterized in that at least one phase consists of a) 0 to 65% by weight of one or more carrier materials, b) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C., c) 0 to 65% by weight of fat (s), d) 0 to 50% by weight of further active substances and / or auxiliaries and e) 0.1 to 70 wt .-% of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts consists. Multi-phase detergent tablet according to Claim 14, characterized in that the phases have the form of layers and the tablet is 2-, 3- or 4-phase. Multi-phase detergent tablet according to claim 14, characterized in that it consists of a base tablet having a cavity and an at least partially contained in the cavity. Multi-phase detergent tablet according to claim 16, characterized in that the part contained in the cavity a) 0 to 10% by weight, preferably 0 to 7.5 and in particular 0 to 5% by weight of one or more carrier materials, b) 30 to 70% by weight, preferably 35 to 65% by weight and in particular 40 to 60% by weight of coating substance (s) with a melting point above 50 ° C., c) 0 to 65% by weight, preferably 10 to 60% by weight and in particular 20 to 50% by weight of fat (s), d) 0 to 50% by weight, preferably 5 to 45% by weight and in particular 10 to 40% by weight of further active substances and / or auxiliaries and e) 0.1 to 70% by weight, preferably 1 to 50% by weight and in particular 5 to 40% by weight, of metal salts of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid other than the alkali metal salts consists. Article for hanging in the dishwasher, comprising a container which has at least one side made of a permeable material and a composition which can escape through the permeable material, characterized in that the composition contains metal salts of an unbranched or branched, unsaturated or saturated, mono- or contains multiply hydroxylated fatty acid with at least 8 carbon atoms and / or a resin acid with the exception of the alkali metal salts. Article according to claim 18, characterized in that the composition contains one or more metal salts of ricinoleic acid and / or abietic acid, preferably zinc ricinoleate and / or zinc abietate, in particular zinc ricinoleate. Article according to one of claims 18 or 19, characterized in that only one side wall of the container is made of permeable material and this side is closed with removable, non-permeable film.