DE10060534A1 - Use of optionally alkoxylated ethanolammonium salts in dishwasher detergents for washing dishes, especially rinse agents or detergent tablets - Google Patents

Abstract

Optionally alkoxylated ethanolammonium salts (I) are used in dishwasher detergents. Cationic compounds of formula (I) are used in dishwasher detergents: AO = alkoxy; R<1> = H or 1-6C alkyl; R<2>-R<4> = H, 1-28C alkyl, 2-28C alkenyl or TR<5>; R<5> = 8-28C alkyl; T = OCO or COO; a, b, c, d, e, f, x, y, z = 0-50; and X = an anion. Independent claims are also included for: (1) a (I)-containing rinse agent for dish washing machines; and (2) a detergent tablet for dish washing machines, comprising builders and optionally other detergent ingredients and including 0.5-60 wt.% (I).

Description

The present invention relates to machine dishwashing detergents and rinse aid for the ma rapid dishwashing, which contain certain cationic surfactants.

Today, machine-washed dishes are often subject to higher requirements than ma newly washed dishes. In this way, dishes that have been completely cleaned of leftovers are then used as not rated correctly if it is still whitish after machine dishwashing Water hardness or other mineral salts has stains that lack mesh medium come from dried water drops.

To obtain dishes that are clear and spotless, rinse aid is therefore used successfully today on. The addition of rinse aid at the end of the wash program ensures that the water is possible Lich runs completely from the dishes, so that the different surfaces at the end of Wash programs are residue-free and spotlessly shiny.

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 clear rinse cycle. The temperature of the main wash cycle varies depending on the machine Type and program level selection between 40 and 65 ° C. In the rinse aid, a do siertank in the machine added rinse aid, which is usually not the main ingredient African surfactants. Such rinse aids are in liquid form and are in the state of the art Technology broadly described. Your job primarily consists of lime stains and toppings to prevent the cleaned dishes. In addition to water and low-foaming non-ionic surfactants These rinse aids often also contain hydrotopes, pH adjusting agents such as citric acid or scale inhibitors polymers.  

Liquid rinse aids are known from EP-B1 0 197 434 (Henkel), which are used as nonionic surfactants Mixed ether included. A variety of different materials are used in the dishwasher (Glass, metal, silver, plastic, porcelain) cleaned. This variety of materials must be rinsed in the rinse cycle be wetted as well as possible. Rinse aid formulations that act exclusively as a surfactant component Containing mixed ethers do not meet these requirements or only to a small extent, so that the Rinse aid or drying effect is unsatisfactory, especially with plastic surfaces.

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. Becomes forget to fill up the tank, especially glasses with limescale and deposits unsightly. In the state of the art there are therefore some proposed solutions, a rinse aid to integrate into the detergent for automatic dishwashing. This solution Blows are tied to the form of the compact body.

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

The object of the present invention was to provide new rinse aid deliver at least the same results as the application properties commercially available rinse aid and the additional performance advantages, especially with Provide drying behavior on the treated surfaces. The new clear dishwasher both as a conventional rinse aid and in the form of combination products be settable and develop their advantageous properties regardless of the form of preparation. Last but not least, the use of the new rinse aid should also be used in conventional detergents be possible for automatic dishwashing, d. H. the funds should also be used as an additional component Enable performance benefits.

It has now been found that the use of certain cationic surfactants in cleaning agents for machine dishwashing has beneficial effects and in particular a shorter drying time time and improved drying performance. It is particularly advantageous if the speci ellen surfactants are used in the rinse aid.

In a first embodiment, the present invention therefore relates to the use of cationic compounds of the formula I.

wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion in dishwashing machines.

The mere addition of these compounds to cleaning agents has the effect that those with such agents treated dishes become significantly cleaner in subsequent cleaning processes than Parts of dishes that have been washed using conventional means. The effect is there independently of whether the automatic dishwashing detergents are in liquid, powder or tablet form.

As an additional positive effect, there is a shortening of the drying time with cleaning medium treated dishes on d. H. the consumer can after 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 comparable agents without the use of alkoxylated cationic surfactants. Before al Plastic surfaces are significantly drier than the treatment according to the invention if they have been treated with conventional means.

In the context of the teaching according to the invention, drying time is generally the literal sense understood appropriate meaning, that is, the time that elapses until one in a dishwasher ne treated dish surface has dried, but especially the time that elapses until 90% be with a detergent or rinse aid in concentrated or diluted form acted surface is dried.

It is particularly advantageous if the alkoxylated cationic surfactants are present in the last rinse cycle, ie in the rinse cycle. In this way, the beneficial effect is not weakened by subsequent rinses. Another object of the invention therefore provides the use of cationic compounds of formula I.

wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion in the rinse aid for machine dishwashing.

Irrespective of whether the use according to the invention is implemented in detergents or rinse aids, certain cationic compounds are preferred. For reasons of simpler illustration, those compounds are preferred, for example, in which the AO groups indicated with a, b, c or d, e, f or x, y, z in formula I are the same groups, as a result of which formula I corresponds accordingly simplified. Particularly preferred alkylene oxide groups are EO and PO groups, so that preferred uses according to the invention are characterized in that cationic compounds of the formula Ia

wherein R ¹ , R ⁶ , R ⁷ , R ^{8 are} independently selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 - Alkyl or alkenyl groups or TR ⁵ ; R ⁵ = C _8-28 -alkyl T = -O-CO- or -CO-O-, m, n and p for integers from 0 to 50 and X ^- for a counterion.

In this formula, R ⁶ , R ⁷ , R ⁸ independently of one another are particularly preferably -H or -CH ₃ . If all of the substituents R ⁶ , R ⁷ , R ^{8 are} H atoms, compounds are obtained which only have EO groups on the central nitrogen atom. Accordingly, uses according to the invention are those in which cationic compounds of the formula Iaa

wherein each group, each group R ² , R ³ , R ^{4 is} independently selected from C _1-28 alkyl or alkenyl groups and m, n and p represent integers from 0 to 50 and X ^{- represents} a counter ion are particularly preferred.

Analogously, all substituents R ⁶ , R ⁷ , R ^{8 can} stand for a methyl group, so that with the exception of the central EO group, only PO groups are present in the molecule. Such uses in which cationic compounds of formula Iab

wherein each group, each group R ² , R ³ , R ^{4 is} independently selected from C _1-28 alkyl or alkenyl groups and m, n and p represent integers from 0 to 50 and X ^{- represents} a counter ion are also preferred.

Regardless of whether compounds of the formulas I, Ia, Iaa and / or Iab are used, uses according to the invention are preferred in which each group R ² , R ³ , R ⁴ is selected independently of one another from -H, -CH ₃ , - CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , - (CH ₂ ) ₃ CH ₃ , -CH (CH ₃ ) - CH ₂ -CH ₃ , -CH ₂ CH (CH ₃ ) -CH ₃ , -C (CH ₃ ) ₃ or - (CH ₂ ) _k -CH ₃ with k = 4, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27 ,

Uses in which each of the numbers a, b, c, d, e, f, x, y, z and m, n, p are independent of one another other for the value 0 or for values from 2 to 40, preferably from 3 to 30 and in particular from 4 to 20 is also particularly preferred - again regardless of whether connection gene of the formulas I, Ia, Iaa and / or Iab are used.

Further particularly preferred representatives from the group of alkoxylated cationic compounds can be described by Formula II:

Here EO = ethylene oxide, R and R 'are identical or different alkyl radicals and n ₁ = 0-30 and n ₂ = 0-30, where A is a counter ion. R can be a (C ₅ -C ₂₆ ) alkyl radical, preferably a (C ₁₂ -C ₂₂ ) tallow alkyl radical and particularly preferably a (C ₁₆ -C ₁₈ ) tallow alkyl radical. R 'can be a (C ₁ -C ₁₀ ) alkyl radical, in particular ethyl. n ₁ and n ₂ can assume identical or non-identical values, each in a range from 0-30, preferably from 1-20, more preferably from 1-16 and particularly preferably from 1-8. For example, they can have the values 10, 12 and / or 14 in particular. The counterion A is a single negatively charged anion, preferably from the group chloride, bromide, iodide, hydroxide, hydrogen sulfate, hydrogen carbonate, dihydrogen phosphate, rhodanide, aryl sulfate and (C ₁ -C ₅ ) alkyl sulfate and is preferably methyl sulfate or ethyl sulfate and particularly preferably ethyl sulfate.

Suitable radicals R are even-numbered and odd-numbered, saturated and unsaturated, unbranched and branched alkyl residues, especially fatty acid alkyl residues, e.g. B. caproic acid alkyl, Caprylic acid alkyl, capric acid alkyl, lauric acid alkyl, myristic acid alkyl, palmitic acid alkyl, stea rinic acid alkyl, arachidic acid alkyl, behenic acid alkyl, lignoceric acid alkyl, cerotic acid alkyl, Valeri acidic alkyl, enanthic acid alkyl, pelargonic acid alkyl, pentadecanoic acid alkyl, margaric acid alkyl, Pristanoic acid alkyl, phytanoic acid alkyl, oleic acid alkyl, erucic acid alkyl, nervonic acid alkyl, linoleic acid realkyl, linolenic acid alkyl, arachidonic acid alkyl, eicosapentaenoic acid alkyl, dicosahaenic acid alkyl, Oleic acid alkyl, palmitoleic acid alkyl, myristoleic acid alkyl, elaidic acid alkyl, linolelaidic acid alkyl, Eleostearic acid alkyl or parinaric acid alkyl.

The radical R 'can be a branched or unbranched alkyl radical, such as. B. decyl, nonyl, Octyl, n-heptyl, (1-6-) methylheptyl, n-hexyl, (1-5-) methylhexyl, n-pentyl, isopentyl, neopentyl, 1- Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylpentyl, 2-ethylpentyl, 3- Ethylpentyl, 1-propylpentyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2,2, -dimethylbutyl, 3,3- Dimethylbutyl, 2,3-dimethylbutyl, 2-ethylbutyl, n-propyl, isopropyl, and especially ethyl.

For the two ethoxylated radicals, z. B. consider the following residues: 2- Hydroxyethyl, ethyleneoxyhydroxyethyl, diethyleneoxyhydroxyethyl, triethyleneoxyhydroxyethyl, Te traethyleneoxyhydroxyethyl, pentaethyleneoxyhydroxyethyl, hexaethyleneoxyhydroxyethyl, Heptae ethyleneoxyhydroxyethyl, octaethyleneoxyhydroxyethyl, nonaethyleneoxyhydroxyethyl, decaethylene oxyhydroxyethyl, undecaethyleneoxyhydroxyethyl, dodecaethyleneoxy-hydroxyethyl, tridecaethy lenoxy-hydroxyethyl, tetradecaethyleneoxy-hydroxyethyl, pentadecaethyleneoxy-hydroxyethyl, He xadecaethyleneoxyhydroxyethyl, etc.  

The quaternary ammonium compound tallow alkyldi (polyethoxy hydroxyethyl) ethylammonium ethyl sulfate (Adogen® 66).

The one or more quaternary ammonium salts of the formulas I (or Ia, Iaa, Iab) and / or II are preferably in an amount of 0.01-10% by weight, preferably 0.05-7% by weight, more preferred 0.05-5% by weight, particularly preferably 0.1-3% by weight and most preferably in an amount of 0.2-2% by weight, based in each case on the agent to be used.

The use according to the invention can be realized in a simple manner in that the ge mentioned substances in liquid, powder or tablet detergents or in rinse aid medium incorporated.

In preferred embodiments of the present invention, the cationic surfactants arrive for use in the rinse cycle of automatic dishwashing. Preferred further execution Forms of the present invention therefore relate to machine rinse aid Dishwashing and combination forms, the detergent and rinse aid together connect, the latter being offered in particular in powder or tablet form.

Another preferred object of the present invention are rinse aids for automatic dishwashing, containing cationic compounds of the formula I.

wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion.

Such rinse aids are ge by the consumer in the storage tank of the dishwasher 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 one or more cationic compounds contains (s) that satisfy the formulas Ia and / or Iaa and / or Iab.  

In an embodiment with a particularly advantageous effect, the clear according to the invention contains detergent the cationic compound (s) in amounts of 0.001 to 20 wt .-%, preferably from 0.01 to 15% by weight, particularly preferably from 0.1 to 10% by weight and in particular from 0.15 up to 5% by weight, each based on the rinse aid.

In addition, the agents according to the invention can be anionic, nonio Contain niche, cationic and / or amphoteric surfactants, with non-ionic surfactants due their foaming power are preferred.

Examples of anionic surfactants used are 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 having an end or internal double bond 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. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyceri nests are to be understood as the mono-, di- and triesters as well as their mixtures, as in the case of the her position by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the Um esterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. Preferred sulfated fat Acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbons Substance atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid re, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and especially 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 these chain lengths 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 analogous to that of the appropriate 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 ten side (description see below). Again, sulfosuccinates, the fatty alcohol residues of which 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, hy third erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. 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 special primary alcohols with 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 is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, Alko holethoxylate with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-14 - 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 in the 2-position methyl branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or 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.

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.

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 Aryl radical or an oxy-alkyl 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 per poxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example wise 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 is converted into the desired polyhydroxy fatty acid amides become.

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

Rinse aids according to the invention which contain a nonionic surfactant are particularly preferred hold that has a melting point above room temperature. As a result, are preferred Rinse aid characterized in that it contains 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, contain.

Suitable non-ionic surfactants, the melting or softening points in the tempera mentioned have low-foaming nonionic surfactants, which at Room temperature can be solid or highly viscous. Become highly viscous at room temperature Nonionic surfactants used, it is preferred that these have a viscosity above 20 Pas, preferably have above 35 Pas and in particular above 40 Pas. Also non-ionic surfactants that are used in Room temperature waxy consistency are 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 more complex tensides such as polyoxypropy len / 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 Reak tion 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 Ethylene oxide per mole of alcohol or alkylphenol has emerged.

A particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol ethylene oxide won. 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 was 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 point. 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 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 propy lenoxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to make up 15% by weight of the total molecular weight of the nonionic surfactant.

Other nonionic surfactants to be used with particular preference with melting points above room temperature temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene Block polymer blends, which is 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 Copolymers of polyoxyethylene and polyoxypropylene, initiated with and containing trimethylolpropane tend 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 is 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. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. 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 group-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula applies

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 C atoms, R ³ stands for 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 is for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18 stands, are particularly preferred.

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 surfactant (s) and in particular nonionic chemical surfactant (s) from the group of alkoxylated alcohols, in amounts of 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 re from 2 to 30 wt .-%, each based on the rinse aid.

In the context of the present invention, non-ionic surfactants and end-capped surfactants and nonionic surfactants with butyloxy groups can also preferably be used. 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, isopropyl, n-butyl, isobutyl or tert -Butyl stands and x can take 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 the R ¹ for 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 _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} .

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. before preferably the solvents are selected from ethanol, n- or 1-propanol, butanols, Gly kol, propane or butanediol, glycerin, diglycol, propyl or butyl diglycol, hexylene glycol, ethyl lenglykolmethylether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Etheylenglykolmono-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 trigly kol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and Mixtures of these solvents, so that preferred rinse aids are characterized in that 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, hexy lenglycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Ethey lenglycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol kolmethyl, 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.  

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. B. at the The assembly of liquid washing or cleaning agents are xylene and cumene sulfonate. Other substances, e.g. B. 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.

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 ^{- represents} 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, isopentyl or neopentyl radical. In general, 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 mono-substituted 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 commercially available toluenesulfonates (ortho- and para-toluenesulfonate), the para-isomer is preferred in the context of the present invention. The para-isopropylbenzenesulfonate is also the preferred compound for 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 N): 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 two se from 0.3 to 5 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the clear detergent, used.

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 acid are available here Ren as well as organic acids, provided that these are compatible with the other ingredients. For reasons of consumer protection and handling safety, in particular solid mono-, oligo- and polycarboxylic acids can be used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumar acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid are can also be used. Commercially available and as an acidifying agent within the scope of the available Sokalan® DCS (trademark of BASF) can also preferably be used according to the invention Mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight). Rinse aid which contains acidifying agents, preferably organic acids particular preference for adipic acid, amidosulfonic acid, succinic acid, citric acid, Fumaric acid, maleic acid, malonic acid, oxalic acid and tartaric acid and mixtures of these acids ren, 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 conventional dishwashers. The preferred use of the genann However, cationic compounds can also be achieved by delaying the dissolution bot 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.

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% by weight of cationic compounds of the formula I.
  wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl - or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and K for stand a counter ion

contains.

All substances which are solid at room temperature are suitable as carrier substances a). usual wise you will choose fabrics that have no additional effect in the cleaning cycle ten, whereby builders are particularly suitable. In preferred carrier material-containing particles shaped rinse aids are substances from the group of water-soluble detergents and detergent ingredients, preferably the carbonates, hydrogen carbonates, sulfates, Phosphates and the organic oligocarboxylic acids solid at room temperature in amounts of 35 up 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, for example pour such a melt can be obtained on the support materials.

The manufacturing processes are described below; a description of the In follows substances 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 following the information on the composition of the mixture / melt applied to the carrier is, the proportion of the particle from the proportions of mixture and carrier material in the Parti kel 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, d. H. 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 gene. 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 be enamel range (solidification range) in such a temperature range at 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. Under "Waxing" is understood to mean a number of natural or artificially derived substances that usually Melt above 40 ° C without decomposition and behaves just above the melting point are viscous and not stringy. They exhibit a strongly temperature-dependent Consistency and solubility.  

According to their origin, the waxes are divided into three groups, the 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. 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 weight fatty acids (wax acids) as the main name Many natural waxes are a component of 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 mg / l at a temperature of about 30 ° C not exceed 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 aid contain one or more substances with egg as the coating substance nem melting range from 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 have one or more contain more fatty substances, preferred rinse aids are characterized in that they as ingredient c) 1 to 60, preferably 5 to 55, particularly preferably 10 to 50 and in particular re 20 to 45 wt .-% fat (s) contain.

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, esp especially the fatty acid esters understood. Reaction products of fatty alcohols with alkylene oxides and the salts of fatty acids are among the surfactants in the context of the present application (see above) and are not fatty substances in the sense of the invention. Fats can be invented According to the invention, fatty alcohols and fatty alcohol mixtures, fatty acids and fatty acid mixtures are preferred cal, fatty acid esters with alkanols or diols or polyols, fatty acid amides, fatty amines etc. deploy.

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 are, for example, the alcohols 1-hexanol (capro alcohol), 1-heptanol (enant alcohol), 1-octanol (capry alcohol), 1-nonanol (pel argon alcohol), 1-decanol (capric alcohol), 1-hexanol (capro alcohol) 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 - octadecadien-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, alcohol mixtures can of course also be used, for example those such as the C _16-18 alcohols prepared by ethylene polymerization according to Ziegler. Specific examples of alcohols which can be used as component c) are the alcohols already mentioned, and lauryl alcohol, palmityl and stearyl alcohol and mixtures of the same.

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 given to 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 carried out last year led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in the car 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 in the context of the present compound is preferred of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexaconic acid (trisotonic acid) and tricotonic acid (melotinic acid) as well as melotinic acid (cerotinic acid) unsaturated species 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-octadtanoic acid, linoleic acid Octadecadienoic acid (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 acid Koskosölfett (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% by weight C ₁₄ , 7% by weight C ₁₆ , 2% by weight C ₁₈ , 15% by weight C _{18 '} , 1% by weight C _18' ), tallow fatty acid (approx 3% by weight of C ₁₄ , 26% by weight of C ₁₆ , 2% by weight of C _{16 '} , 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44% by weight C _{18 '} , 3% by weight C _18' , 1% by weight C _{18 '''} ), hardened tallow fatty acid (approx 2% by weight of C ₁₄ , 28% by weight of C ₁₆ , 2% by weight of C ₁₇ , 63% by weight of C _{18 '} , 1% by weight of C _18' ), technical oleic acid (approx. 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 wt .-% C _{16 ',} 1 wt .-% C _17, 2 wt .-% C _18, 70 percent % C _{18 '} , 10% by weight C _18' , 0.5% by weight C _{18 '''} ), technical palmitin / stearic acid (approx. 1% by weight C ₁₂ , 2% by weight C ₁₄ , 45% by weight C ₁₆ , 2% by weight C ₁₇ , 47% by weight C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15% 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 set, with fatty acid polyol esters being preferred. The fatty acid polyol esters are mono- or 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 before moves 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 Ge Mixtures of acids with 16 to 18 carbon atoms such as tallow fatty acid are for esterification suitable with the polyhydric alcohols. As polyols with the aforementioned fatty acid ren are esterified, come within the scope of the present invention sorbitol, trimethylolpropane, Neopentyl glycol, ethylene glycol, polyethylene glycols, glycerin and polyglycerols.

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

The particulate rinse aid according to the invention can preferably be wide as ingredient d) re active and / or auxiliary substances from the groups of surfactants, bleaches, bleach activators, should release polymers, enzymes, silver preservatives, complexing agents, dyes and fragrances in quantities  from 0 to 50% by weight, preferably from 2.5 to 45% by weight, particularly preferably from 5 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 be Preferred particulate rinse aid are characterized in that they contain as ingredient d) in addition surfactant (s), preferably nonionic surfactant (s), particularly preferably those from the Group of alkoxylated alcohols, in amounts of 5 to 47.5% by weight, preferably 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 that are used as component d) in the clear according to the invention dishwasher can be incorporated are described in detail below.

As ingredient e), the particulate rinse aid according to the invention contains the inventive According to cationic surfactants used, the above statements regarding be preferred species apply completely analogously. To avoid redundancies, therefore, the above mentioned formulas. Preferred particulate rinse aid contain one or several cationic compound (s) 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, each based on the particulate rinse aid, which is represented by the formulas I and / or Ia and / or have Iaa and / or Iab described.

Another object of the present invention is a process for the production of detergent components in the form of particles, which is characterized in that a melt is formed

• 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, preferably 1 to 50% by weight and in particular 5 to 40% by weight of cationic compounds of the formula I.
  wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl- or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion,

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, Ver preferred driving variants, in which the meltable substance, 25 to 85 wt .-%, preferably se 30 to 70 wt .-% and in particular 40 to 50 wt .-% of the melt.

The melt can be applied to the carrier material in all conventional mixing devices be carried out. The shaping processing step for the mixture of melt ze and carrier material is also not subject to any procedural restrictions, so that the person skilled in the art can also select from the methods familiar to him. When trying the Applicants have found processes to be preferred in which the shaping process processing by granulating, compacting, pelleting, extruding or tableting.

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 in varying amounts be contained in the resulting rinse aid particles. Preferred methods are thereby characterized in that a mixture of 5 to 50 wt .-%, preferably 10 to 45 wt .-%, be 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 .-%, especially before adds 60 to 85% by weight and in particular 65 to 80% by weight of carrier material (s) to give shape will work.

Regarding the ingredients used in the method according to the invention and the inventions are processed according to the carrier material-based detergent components analogous to what was said 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 manufacturing particulate Detergent components according to the invention have in particular the Ver prilling, pastilling and scaling by means of chill rolls proven.  

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, preferably 1 to 50% by weight and in particular 5 to 40% by weight of cationic compounds of the formula I. wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl- or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion,

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 according to 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.

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 formed

• 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, preferably 1 to 50% by weight and in particular 5 to 40% by weight, of cationic compounds of the formula I.
  wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl- or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion,

dosed on chilled pastilles.

Pastilling, which is sometimes referred to as pelleting, includes the dosage of Melt from the ingredients a) to d) on rotating, inclined plates that have a temperature un have below the melting temperature of the melt and preferably below room temperature be cooled. Here too, process variants can be carried out in which the Pa breastfeeding plates are frozen. However, measures must be taken to prevent condensation be hit by humidity.

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

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, preferably 1 to 50% by weight and in particular 5 to 40% by weight of cationic compounds of the formula I.
  wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl- or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion,

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

The use of cooling rollers enables the desired particle to be easily adjusted size range, in this method according to the invention also below 1 mm, for example as 200 to 700 microns, may be.

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 according to the invention in particulate machine dishwashing to mix in.

Another object of the present invention is therefore also a particulate machine normal dishwashing detergent, containing builders and optionally other ingredients from the Groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, Dyes and fragrances containing a particulate rinse aid according to the invention in amounts of 0.5 up to 30% by weight, preferably from 1 to 25% by weight and in particular from 5 to 15% by weight, in each case based on total mean.

The ingredients of automatic dishwashing detergents are described below. Partly these can also be used as active substances or carrier materials in the clear according to the invention dishwasher particles are included.

The most important ingredients in automatic dishwashing detergents are builders. In the inventions Detergents according to the invention for machine dishwashing can all be more common builders used in detergents and cleaning agents, in particular  So zeolites, silicates, carbonates, organic cobuilders and - if no ecological concerns exist against their use - also the phosphates. The builders listed below are all suitable as carrier materials for the rinse aid particles according to the invention, as already was carried out 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. 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 Na ₂ O: SiO ₂ modulus from 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. which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amor phen 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 provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products mikro 79689 00070 552 001000280000000200012000285917957800040 0002010060534 00004 79570 crystal regions have sizes from 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. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

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 Cros field) 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. 80% by weight zeolite X), which was developed by CONDEA Auguste S. p. A. is sold under the brand name VEGOBOND AX® and through 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 industry the most important.

Alkali metal phosphates is the summary 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, very easily soluble in water powder, which lose the 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 trime taphosphate (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 easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated more. 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 that have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition) as dodecahydrate, as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (accordingly 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under 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 three-phase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when 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) , In the case of substances, there are colorless crystals which are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, graham 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 a non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n which crystallizes with 6H ₂ O and is water-free -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 60 ° approx. 20 g, at 100 ° about 32 g of the water free of crystal water; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

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

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or Mi combinations of these two can be used; also mixtures of sodium tripolyphosphate and natri umkaliumtripolyphosphat or mixtures of potassium tripolyphosphate and sodium potassium tripoly phosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium Umtripolyphosphate 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 settable polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function. For example, these are citric acid, adipin acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acid ren, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these. Preferred salts are the salts 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. In addition to their builder, the acids possess typically also have the property of an acidifying component and are therefore also used for Setting a lower and milder pH value for detergents or cleaning agents. in particular citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metals tall 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), a UV detector being used.

The measurement was made against an external polyacrylic acid standard, which due to its structural relationship to the investigated polymers provides realistic molecular weight values. This information differs significantly from the molecular weight information for which polystyrene sulfonic acid be used as standard. The molar masses measured against polystyrene sulfonic acids are usually 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 acid ren, is generally 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and ins special 30,000 to 40,000 g / mol.

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

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

Also particularly preferred are biodegradable polymers made from more than two different ones NEN monomer units, for example those which are salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those which are preferably monomers acrolein and acrylic have 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 and glutaral dehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates 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. The hydrolysis products are preferably of medium molar mass range from 400 to 500000 g / mol. A polysaccharide with a dextrose Equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being one 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.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine di succinate, are other suitable cobuilders. Here, ethylenediamine-N, N'-disuccinate (EDDS) be preferably used in the form of its sodium or magnesium salts. Also preferred are in in this connection also glycerol disuccinates and glycerol trisuccinates. Suitable use Quantities in formulations containing zeolite and / or silicate are 3 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 are at least at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the hydroxyal Kanphosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt is alkaline (pH 9). As aminoalkane phosphonates occur preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate  (DTPMP) and their higher homologues in question. They are preferably in shape the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta and Octa sodium salt of DTPMP, used. As a builder, the class of phosphonates preferably HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also contains lead che contain, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth ions to be used as cobuilders.

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

Of the compounds used as bleaching agents and providing H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Detergents according to the invention can also contain bleaches from the group of organic bleaches. Typical organic bleaching agents are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxy acid piperoxyaproacid acid (ε-phthalimidanoic acid), )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocytes sebacic acid, diperoxydiperoxyboxyldiperoxyboxyldiperoxyboxyldiperoxybutyldiacyldiperoxybutylacid, 1,4-diacid, N, N-terephthaloyl-di (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, 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 machine according to the invention normal 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 gene containing one or more N- or O-acyl groups, such as substances from the class of Anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraace tylethylene diamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhexylene diamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and Isatoic anhydride ISA.

As bleach activators, compounds which are aliphatic under perhydrolysis conditions oxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or result in optionally substituted perbenzoic acid can be used. Substans are suitable zen, the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substi tuated benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, ins special n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid hydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triace tin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA) as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), penta acetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N- alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N- Benzoyl. Hydrophilically substituted acylacetals and acyllactams are also considered trains used. Combinations of conventional bleach activators can also be used.

In addition to the conventional bleach activators or in their place, so-called called bleaching catalysts are incorporated into the rinse aid particles. With these substances han it is 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 and Co, Fe, Cu and Ru-amine complexes can be used as bleaching catalysts.  

Bleach activators from the group of multi-acylated alkylenediamines, in particular, are preferred special 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 men gene up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and be 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 of manganese and / or cobalt salts ze and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) - Complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese Sulfates are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, each based on the total agent used. But in special cases, more can be done 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 of these hydro Lases help to remove stains such as stains containing protein, fat or starch kung at. Oxidoreductases can also be used for bleaching. Particularly suitable are from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified Variants of enzymatic active ingredients obtained. Proteases from subtilisin are preferably Type and in particular proteases obtained from Bacillus lentus. there are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active Enzymes or protease, lipase or lipolytic enzymes, but especially Pro tease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of special interest. Examples of such fipofytic enzymes are the known ones Cutinases. Peroxidases or oxidases have also proven to be 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 percentage of enzymes, enzyme mixtures or En zymgranulate 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 are to improve the aesthetic impression of the resulting products and the Ver besides performance, users need a visually and sensory "typical and distinctive" pro to provide products. Individual fragrance compounds can be used as perfume oils or fragrances gene, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone type. Alcohols and Hydrocarbons are used. Fragrance compounds of the ester type are e.g. B. Ben cyanoacetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbene cylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example se benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, Citral, Citro nellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal the ketones e.g. B. the Jonone, α-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbon substances mainly include terpenes such as limes and pinene. However, Wed are preferred uses different fragrances, which together give an appealing fragrance witness. Such perfume oils can also contain natural fragrance mixtures such as those from plant sources are accessible, e.g. B. 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 labdanu möl 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 limit the liability of Par reinforce foams on the laundry and through a slower fragrance release for long-lasting The scent of the textiles Cyclodextrins, for example, have become such carrier materials proven, with the cyclodextrin-perfume complexes additionally with other auxiliaries can be layered. Also incorporating the fragrances into the clear according to the invention Dishwasher particles are possible and lead to a scent impression when the machine is opened (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 alkylami notriazoles and the transition metal salts or complexes are used. Particularly preferred benzotriazole and / or alkylaminotriazole are to be used. One finds in cleaner formulations In addition, agents often containing active chlorine, which clearly corrode the silver surface can reduce. Chlorine-free cleaners especially contain oxygen and nitrogen organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives thereof Classes of compounds. Also salt-like and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. The over are preferred here gear metal salts, which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware the.

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 subordinate dissolve. This ensures that the active substances are only released in the final rinse cycle be set and develop their effect here. In addition to this chemical packaging is Depending on the type of dishwasher, physical assembly is required so that the Rinse aid particles are not pumped out when the water is changed in the machine and thus the Rinse aid is no longer available. Household dishwashers included before the drain pump, which the water or the cleaning solution after the individual Reini pumps out of the machine, a sieve insert that clogs the pump Prevent dirt residues. If heavily soiled dishes are washed by the consumer, then must this screen insert can be cleaned regularly, which is due to the easy accessibility and Removability is easily possible. The rinse aid particles according to the invention are now in terms of their size and shape preferably designed so that they use the Ge Dishwasher even after the cleaning cycle, d. H. after exercise due to movement Machine and the cleaning solution, do not happen. This ensures that in the rinse aid rinse aid particles in the dishwasher, which are under the the warmer water release the active substance (s) and the desired rinse aid effect bring. Particulate machine dishes preferred in the context of the present invention Detergents are characterized in that the particulate rinse aid has particle sizes between rule 1 and 40 mm, preferably between 1.5 and 30 mm and in particular between 2 and 20 mm having.  

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, the large detergent and clear dishwasher particles. Especially when the rinse aid particles according to the invention are colored are, for example a red, blue, green or yellow color, it is for the Appearance of the product, d. H. of the entire cleaning agent is an advantage if the clear dishwasher particles are visibly larger than the matrix of the particles of the other ingredients of 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. Since the rinse aid particles are produced using a technically uncomplicated process can be used, it is easily possible to use them in the most varied of formats offer men. In addition to the particle shape, which has an approximately spherical shape, for example cylindrical or cube-shaped particles can be produced and used. Other geometric shapes can be realized. Special product designs can, for example, have asterisks shaped rinse aid particles included. Also discs or shapes that plant as a base and carcasses such as tree, flower, flower, sheep, fish, etc. are easy produced. Interesting visual incentives can also be created in this way by the fact that the rinse aid particles are made in the form of a stylized glass to ensure that the rinse aid effect is also To underline the product optically. There are no limits to your imagination.

If the cleaning agents according to the invention are formulated as a powder mixture, in particular especially with very different sizes of rinse aid particles and detergent matrix - on the one hand, partial segregation can occur when the package is shaken, on the other hand the dosage in two successive cleaning cycles may be different because the Ver need not always dose the same amount of detergent and rinse aid particles. Should This can be desired to technically always use the same amount per cleaning cycle about the packaging of the agents according to the invention in sachets from what is familiar to the person skilled in the art water-soluble film can be realized. Also particulate machine dishwashing detergents in which a dosing unit is welded into a bag made of water-soluble film, are counter stood of the present invention.

As a result, the consumer only has one bag which, for example, contains a detergent Contains powder and several optically prominent rinse aid particles in the dispenser  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. On Process for the manufacture of powdered automatic dishwashing detergents with which is a powdered dishwasher detergent known per se with inventive Rinse aid particles are mixed is therefore a further object of the present invention.

The desired retention of the rinse aid particles in the machine described above even with water changes, apart from the above-mentioned enlargement of the rinse aid particles can also be achieved by reducing the holes in the sieve insert. That way you can formulate automatic dishwashing detergents that have a uniform mean particle size, which is smaller than, for example, 4 to 12 mm. For this purpose, the product according to the invention, in which the rinse aid particles also have smaller particle sizes, a sieve insert is included ben that replaces or covers the insert in the machine. Another item The present invention is therefore a kit-of-parts, which is a powdered according to the invention machine dishwashing detergent and a sieve insert for household dishwashers summarizes.

As already mentioned, the combination of middle and sieve insert according to the invention allows Formulation of agents in which the rinse aid particles also have smaller particle sizes sen. Kits-of-parts according to the invention, in which the particle sizes of the machine dishes detergent (taking into account the rinse aid particles) in the range from 400 to 2500 µm preferably from 500 to 1600 microns and especially from 600 to 1200 microns are before Trains t.

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 preferred parts where the mesh size or hole size of the sieve insert be 1 to 4 mm carries and the rinse aid particles are larger than this mesh size or hole size of the sieve record.

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 fictional also possible and preferred according to the kit-of-parts to include a sieve insert, the shape of a basket, which in a known manner in the dishwasher - for example on the cutlery basket - can be hung. In this way, one replaced in such a way designed sieve insert the dosing chamber, d. H. the consumer doses the machine according to the invention  Dishwashing detergent directly in this sieve insert, which in the cleaning and rinse cycle acts as described above.

The advantages according to the invention can also be used in the form of the compact molded article. Another object of the present invention is therefore also a detergent tablets for machine dishwashing, containing builders and optionally further ingredients of detergents, the one or more cationic compound (s) of the formula I.

wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion, 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 , each based on the weight of the molded body.

Here, too, reference can be made to the above information with regard to preferred embodiments will be. As already mentioned, the introduction of the ka to be used according to the invention ionic surfactants in the rinse aid are particularly preferred, so that preferred cleaning agents shaped bodies are characterized in that they dissolve the cationic compound (s) in hesitant form included.

Not only is a release delay particularly preferred here, but a controlled release set tion, which is not based on slower solubility, but on freedom controlled by external circumstances setting is based. The rinse aid particles described above can also be used as shaped bodies be formulated and also offer the possibility of temperature-controlled in molded articles Release of the cationic compounds to be used according to the invention.

Another object of the present invention are therefore multi-phase detergent tablets for machine dishwashing, containing builders and optionally other 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% by weight of cationic compounds of the formula I.
  wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl- or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion,

consists.

Diesel are completely analogous to the above explanations regarding the particulate rinse aid ben embodiments (amount, type and packaging of the ingredients, etc.) also in the Shaped bodies according to the invention preferred.

The individual phases of the molded body can be within the scope of the present invention have different spatial shapes. The simplest possible implementation is two or multilayer tablets, each layer of the shaped body representing a phase. It is but also possible according to the invention to produce multi-phase molded articles in which individual Phases in the form of inclusions in another phase (s). In addition to so-called "Ring-core tablets" are, for example, coated tablets or combinations of these th embodiments possible. Examples of multi-phase moldings can be found in the diagram EP-A-0 055 100 (Jeyes) which describes toilet cleaning blocks. The technically the The most widespread spatial form of multi-phase tablets is the two- or multi-layer tablet. in the 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 molded body is 2-, 3- or 4-phase.

The moldings according to the invention can assume any geometric shape, in particular special concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical drical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octa cathedral, conical, pyramidal, ellipsoid, pentagonal, hexagonal and octagonal prismatic as well as rhombo hedrical forms are preferred. Also completely irregular base areas like arrow or animal shapes, Trees, clouds, etc. can be realized. The shaped bodies according to the invention have corners  and edges, they are preferably rounded. As an additional optical differentiation is an embodiment with rounded corners and beveled ("chamfered") edges vorzugt.

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, Ba Manufacture sisformkörper, which have one or more cavity (s) and the melt the ingredients a) to d) of the detergent component according to the invention into the cavity fill in and freeze there. This manufacturing process gives rise to pulled multiphase detergent tablets, which consist of a base tablet which has a Ka vity, 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. You can cut through the molded body, d. H. an opening on different sides, at have for example on the top and bottom of the molded body, but it can also not be through the entire molded body, the opening of only one molded body side is visible. The shape of the cavity can also be freely selected within wide limits. Out For reasons of process economy, there are through holes, the openings of which are adjacent to one another lie opposite surfaces of the molded body, and troughs with an opening on a mold body side proven. In preferred detergent tablets, the cavity has the Form a through hole, the openings of which are located at two opposite Molded surfaces are located. The shape of such a through hole can be chosen freely are, wherein shaped bodies are preferred in which the through hole is circular, ellipses shaped, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or eight has angular horizontal sections. Also completely irregular hole shapes like arrow or animal shapes, Trees, clouds, etc. can be realized. As with the moldings in the case of square holes 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 a circle can be made round holes are produced as well as round shaped bodies with octagonal holes, whereby there are no limits to the variety of possible combinations. For reasons of procedure economy and aesthetic consumer perception are shaped bodies with holes preferred, in which the shaped body base and the hole cross-section have the same geometri form, for example shaped bodies with a square base and centrally integrated finished square hole. Ring moldings are particularly preferred, i. H. 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 cleaning according to the invention Molded-body articles in which the cavity has the shape of a depression are also imminent Trains t. As with the "hole moldings", the moldings according to the invention can also be used in this Embodiment take any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal and octagonal-prismatic and rhombohedral shapes preferred are. Completely irregular base areas such as arrow or animal shapes, trees, clouds etc. can also be used will be realized. If the molding has corners and edges, these are preferably abge rounds. An embodiment with rounded corners is an additional optical differentiation and chamfered ("chamfered") edges are 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, cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahe drale, conical, pyramidal, ellipsoid, five-, seven- and octagonal-prismatic as well as rhombo can assume a hedrical form. Also completely irregular trough shapes like arrow or animal shapes, Trees, clouds, etc. can be realized. As with the molded bodies, troughs are included rounded corners and edges or with rounded corners and chamfered edges preferred.

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 wt .-%, preferably 0 to 7.5 and in particular 0 to 5 wt .-% of one or several carrier materials,
• b) 30 to 70% by weight, preferably 35 to 65% by weight and in particular 40 to 60% by weight Envelope (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 Lipid (s),
• d) 0 to 50% by weight, preferably 5 to 45% by weight and in particular 10 to 40% by weight further active substances and / or auxiliary substances as well
• e) 0.1 to 70 wt .-%, preferably 1 to 50 wt .-% and in particular 5 to 40 wt .-% cationic compounds of formula I.
  wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl - or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion,

consists.

The recipes described above can vary depending on the content of carriers and amounts melted on the individual ingredients and entered into the cavity as a melt the one where they solidify to the part contained in the cavity. But it is also possible, this or that Metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid with at least 16 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 intermediaries are stuck.

Alternatively, the prefabricated core can be fed to a tablet press and there with another part Chen-shaped premixes can be pressed into a tablet, the premix dose tion so that the core is added to the premix already metered into the die or that the premix is filled onto the core placed in the die. In the first case you get a so-called dot tablet, the core of which is visible on the top, while the the second procedure delivers corresponding tablets rotated by 180 °. Dosed before and after adding the core to the matrix, the core will be completely formed by the enclosed the tablet and you get so-called core coated tablets.

Corresponding processes for the production of so-called point tablets and core-coated tablets ten 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. Detergent tablets are independent of their intended use preferred, in which the volume ratio of the pressed part ("base molding") to Reini agent 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 be specified are given, the two values on the densities of the base molding or the Reini correlate with each other. Regardless of the density of the individual parts detergent tablets according to the invention are preferred in which the Ge 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.

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 detergents or cleaning agents Shaped bodies preferred, in which the surface of the cleaning agent com 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 optically different colored bar. In addition to the optical differentiation, application technology advantages can be achieved by different solubilities of the different shaped body areas can be achieved. Washing and Detergent tablets in which the detergent component dissolves faster than that Base moldings are preferred according to the invention. By incorporating certain components on the one hand, the solubility of the detergent component can be accelerated in a targeted manner, on the other hand, the release of certain ingredients from the detergent component can Advantages in the washing or cleaning process.

Of course, detergent tablets according to the invention are also before where the detergent component dissolves later in the wash program than the base shape body. Performance benefits from this delayed release can be seen, for example achieve that with the help of a slower soluble detergent component Aktivsub punch (s) are only released in later rinses. For example, with the maschi normal dishwashing can be achieved by detergent components that dissolve more slowly, that further active substance (s) are / are available in the rinse cycle. By additional Substances such as nonionic surfactants, acidifying agents, soil release polymers, etc. can be so improve rinse aid results. Incorporation of perfume is also possible without any problems; due to its delayed release, the "Lau gen odor "when opening the machine. The ingredients acidifying agent, soil release polymers  etc. are related to the detergent components of the invention then 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 preferred according to the invention ,

In order to facilitate the disintegration of highly compressed moldings, it is possible to use disintegration aids agents, so-called tablet disintegrants, to be incorporated into them in order to shorten the disintegration times Zen. According to Rompp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182- 184) Excipients understood for the rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in an absorbable form.

These substances, which are also called "explosives" due to their effect, enlarge their volume in the event of water ingress, with the volume on the one hand increasing (swelling) and the other on the other hand, a pressure can be generated via the release of gases, which the tablet in lets smaller particles disintegrate. Well-known disintegration aids are, for example, carbo nat / citric acid systems, whereby other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrro lidon (PVP) or natural polymers or modified natural substances 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 auxiliaries, in each case bezo on the molded body weight. Contains only the basic molding disintegration aid, so The information given relates only to the weight of the base molding. At the incorpo ration of disintegration aids in the detergent components according to the invention count those as ingredient d).

Disintegration agents 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. 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, carboxy methyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used solely as cellulose-based disintegrants, 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. Particular preference is given to using cellulose-based disintegration agent pure cellulose which is free from cellulose derivatives.

The cellulose used as disintegration aid is preferably not in finely divided form used, but before mixing into the premixes to be pressed into a coarser one Form transferred, for example granulated or compacted. Detergent tablets per, which contain disintegrants in granular or optionally cogranulated form, are in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO 98/40463 (Henkel). These writings are also more details on the production of granulated, compacted or cogranulated cellulo to remove disintegrant. The particle sizes of such disintegrants are mostly above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and esp in particular at least 90% by weight between 400 and 1200 µm. The above and in the coarser described disintegration aids based on cellulose are preferably used as disintegration aids in the context of the present invention and commercially, for example, under the name Arbocel® TF-30-HG from Retten maier available.

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 and completely dissolve 30% of the total cellulose mass) of the celluloses, which crystallize leave areas (approx. 70%) undamaged. A subsequent disaggregation of the the hydrolysis of the microfine celluloses produces the microcrystalline celluloses, the Pri have particle sizes of about 5 µm and, for example, granules with a medium Particle size of 200 microns can be compacted.  

Preferred detergent tablets contain additional Lich a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on on the molded body weight.

The detergent tablets according to the invention can moreover both in the basic form body as well as in the detergent component contain a gas-developing shower system. The gas-evolving shower system can consist of a single substance that is in contact releases a gas with water. Among these compounds is magnesium peroxide in particular to name, which releases oxygen on contact with water. This is usually gas-free however, the bubbling system itself consists of at least two components that work together react with gas formation. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, will be invented bubble system used according to the detergent tablets according to the invention hand selected more economically and based on ecological considerations. preferred Shower systems consist of alkali metal carbonate and / or hydrogen carbonate and an Aci dififying agent which is suitable from the alkali metal salts in aqueous solution carbon dioxide release.

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 from washtech African interest may be preferred.

In preferred shaped detergent bodies, 2 to 20% by weight are preferred as the shower system example 3 to 15 wt .-% and in particular 5 to 10 wt .-% of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight of egg Acidifying agent used, 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 acidification is preferred agent used, the citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. From this group tartaric acid, succinic acid, malonic acid, adipic acid are preferred right, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as ami Dosulfonic acid can also be used. Commercially available and as an acidifier in  Within the scope of the present invention, Sokalan® DCS (Warenzei BASF), a mixture of succinic acid (max. 31 wt.%), glutaric acid (max. 50 wt. %) 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 oli gocarboxylic acids or mixtures of these are used.

The particulate detergents and / or detergents and cleansing agents can, like the detergent components according to the invention, be packaged after manufacture, the use of certain packaging systems having proven particularly useful. Another aspect of the present invention is a combination of (a) particulate cleaning agent (s) according to the invention and / or (a) inventive laundry detergent or cleaning product tablet (s) and a packaging system containing the cleaning agent and / or the washing and cleaning product tablets 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 transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day, if the 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 DIN standard 53122, whereby according to DIN 53122 minimal deviations are permissible (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 measurement 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. 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, the moisture vapor permeability rate can be reduced

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 mist (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 the laboratory moisture control to +/- 2% r. Adjust L. exactly. Also about ge saturated solutions of certain salts form in closed systems at a given temperature constant and well-defined relative air humidity, which is based on the phase Balance between partial pressure of water, saturated solution and soil body.

The combinations according to the invention can of course in turn in secondary packaging kung, for example cardboard boxes or trays, are packed, with the secondary packaging no further requirements have to be made. The secondary packaging is that if 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 the design form of the invention a certain amount of detergent component according to the invention, a certain amount of a particulate detergent composition or one or several detergent tablets. It is preferred according to the invention ent neither to allow a shaped body such that it is an application unit of the washing and Detergent includes, and to package this molded article individually, or the number of form body to pack in a packaging unit, which in total comprises an application unit. With a nominal dosage of 80 g of detergent and cleaning agent, it is therefore possible according to the invention  produce an 80 g heavy detergent tablet and individually pack, but it is also possible according to the invention, two 40 g washing and cleaning Packing agent in a package to form a combination according to the invention nation to arrive. This principle can of course be extended so that the invention Combinations also three, four, five or even more detergent tablets in can contain a packaging unit. Of course, two or more molded articles have different compositions in one package. That way it is possible to spatially separate certain components from each other, for example, stability to avoid 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. H. 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 rice Fill detergent tablets individually or in groups in sacks or bags. For one individual application units of the detergent tablets, which are in a sack or bags, the term "flow pack" has become established in technology. Such "flow packs "can then - again preferably sorted - optionally packed in outer packaging be what the compact shape of the molded body underlines.

The sacks or bags made of single-layer or laminated paper or plastic film, which are preferably to be 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 caused by heat (hot fusion), adhesives or adhesive tapes be closed. The known papers, which can optionally be impregnated, as well as plastic films, which can optionally be coextruded, are layered bag or sack materials. Plastic films that can be used in the context of the present invention as a packaging system are given, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193. Fig. 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 Ver a sack or bag made of single-layer or laminated plastic film with a  Thickness from 10 to 200 microns, preferably from 20 to 100 microns and in particular from 25 to 50 microns.

Although it is possible to use wax-coated Pa in addition to the films or papers mentioned piere in the form of cardboard boxes as a packaging system for the detergent and cleaning agent form To use body, it is preferred in the context of the present invention if the Verpac system does not include boxes made of wax-coated paper. The term "packaging sy stem always characterizes the primary packaging of the present invention Detergent component, detergent composition or molded article, d. H. the ver pack that directly on the inside with the detergent component, detergent composition or molded body surface is in contact. An optional secondary packaging there are no requirements, so that all common materials and systems are used can be set.

As already mentioned above, the detergent components contain detergents compositions or detergent tablets of the combination according to the invention nation, depending on its intended use, further ingredients of detergents and cleaning agents in varying amounts. It is independent of the intended use of the agent or molded article preferred according to the invention that the agent or agents or detergents and cleaning agents moldings have a relative equilibrium moisture content of less than 30% at 35 ° C has / have.

The relative equilibrium moisture content of the detergent or detergent tablets can be determined using common methods, whereby within the scope of this sub The following procedure was chosen: A water-impermeable 1 liter container with a lid, which has a closable opening for introducing samples filled with a total of 300 g detergent tablets and 24 hours at a constant 23 ° C held to ensure a constant temperature of the vessel and substance. The what The steam pressure in the space above the molded body can then be measured using a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now ge every 10 minutes Measure until two successive values show no deviation (equilibrium moisture ness). The above Hygrometer allows a direct display of the recorded 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 in which the ver packaging system has a microperforation, can be realized according to the invention with preference ren.  

As mentioned above, detergent components, detergents can be combined settlements or detergent tablets for automatic dishwashing according to the inventions produce the method according to the invention. Accordingly, a cleaning process is for cleaning of dishes in a dishwasher, characterized in that one or more Particulate detergent according to the invention and / or one or more inventions the detergent tablets according to the invention the dosing chamber of the dishwasher inserted and a rinsing program can run, in the course of which the dosing chamber opens and the detergent or detergents and / or the molded article or articles are dissolved, another Subject 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 composition according to the invention tongues or the shaped body or bodies according to the invention for example in the cutlery basket Insert. Of course, the use of a dosing aid, for example one, is also here Basket, which is attached in the sink, easily possible. Accordingly, a Rei cleaning process for cleaning dishes in a dishwasher, characterized records that one or more particulate detergent according to the invention and / or one or more shaped tablets according to the invention or in the dishwasher's washing compartment without a dosing aid and run a washing program can, in the course of which the cleaning agent or detergents and / or the molded body or the dissolved are another object of the present invention.

Claims (25)

1. Use of cationic compounds of formula I.
wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl- or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion, in automatic dishwashing detergents. 2. Use of cationic compounds of formula I.
wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl- or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion, in the rinse aid in automatic dishwashing. 3. Use according to one of claims 1 or 2, characterized in that cationic compounds of formula Ia
wherein R ¹ , R ⁶ , R ⁷ , R ^{8 are} independently selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 - Alkyl or alkenyl groups or TR ⁵ ; R ⁵ = C _8-28 -alkyl T = -O-CO- or -CO-O-, m, n and p for integers from 0 to 50 and X ^- for a counterion. 4. Use according to claim 3, characterized in that cationic compounds of the formula Iaa
wherein each group, each group R ² , R ³ , R ^{4 is} selected independently of one another from C _1-28 - alkyl or alkenyl groups and m, n and p represent integers from 0 to 50 and X ^{- represents} a gene, be used. 5. Use according to claim 3, characterized in that cationic compounds of formula Iab
wherein each group, each group R ² , R ³ , R ^{4 is} selected independently of one another from C _1-28 - alkyl or alkenyl groups and m, n and p represent integers from 0 to 50 and X ^{- represents} a gene, be used. 6. Use according to one of claims 1 to 5, characterized in that each group R ² , R ³ , R ^{4 is} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , - (CH ₂ ) ₃ CH ₃ , -CH (CH ₃ ) -CH ₂ -CH ₃ , -CH ₂ CH (CH ₃ ) -CH ₃ , -C (CH ₃ ) ₃ or - (CH ₂ ) _k -CH ₃ with k = 4, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27. 7. Use according to one of claims 1 to 6, characterized in that each of the numbers a, b, c, d, e, f, x, y, z and m, n, p independently of one another for the value 0 or for values of 2 to 40, preferably from 3 to 30 and in particular from 4 to 20. 8. Rinse aid for automatic dishwashing, containing cationic compounds of the formula I.
wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl- or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion. 9. rinse aid according to claim 8, characterized in that it is one or more cationic Contains compound (s) which satisfy the formulas Ia and / or Iaa and / or Iab. 10. rinse aid according to one of claims 8 or 9, characterized in that it is the katio African compound (s) in amounts from 0.001 to 20% by weight, preferably from 0.01 to 15% by weight, particularly preferably from 0.1 to 10% by weight and in particular from 0.15 to 5 wt .-%, each based on the rinse aid contains. 11. rinse aid according to one of claims 8 to 10, characterized in that it is surfactant (s), preferably nonionic surfactant (s) and in particular nonionic surfactant (s) from the Group of alkoxylated alcohols, in amounts from 0.1 to 60% by weight, preferably from 0.5 up to 50% by weight, particularly preferably from 1 to 40% by weight, and in particular from 2 to 30 wt .-%, each based on the rinse aid contains. 12. Rinse aid according to one of claims 8 to 11, characterized in that it is non-aqueous some 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, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycols ethyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy  or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol contains t-butyl ether and mixtures of these solvents. 13. Rinse aid according to one of claims 8 to 12, characterized in that it is a solubilizer, 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 ^{- represents} a cation. 14. Rinse aid according to one of claims 8 to 13, characterized in that it is acidification agents, preferably organic acids with particular preference for adipic acid, Amidosulfonic acid, succinic acid, citric acid, fumaric acid, maleic acid, malonic acid, Contains oxalic acid and tartaric acid and mixtures of these acids. 15. Rinse aid according to one of claims 8 to 14, characterized in that it is additionally one or more substances from the groups of soil release polymers, dyes and Contains fragrances. 16. 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% by weight of cationic compounds of the formula I.
  wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl - or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion,

contains. 17. Particulate rinse aid according to claim 16, characterized in that it has one or several cationic compound (s) in amounts of 0.5 to 60% by weight, preferably of 1 up to 50% by weight, particularly preferably from 2.5 to 40% by weight and in particular from 5 to 30% by weight, each based on the particulate rinse aid, which is characterized by the For Let I and / or Ia and / or Iaa and / or Iab describe. 18. Particulate rinse aid according to one of claims 16 or 17, characterized in that 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, paraffin waxes with a melting range of 50 ° C to 65 ° C and / or substances preferred from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) Envelopes are. 19. Particulate rinse aid according to one of claims 16 to 18, characterized in that he additionally contains surfactant (s), preferably nonionic surfactant (s), as ingredient d), in particular preferably those from the group of 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, contains. 20. Detergent tablets for machine dishwashing, containing builders and optionally further ingredients of detergents, characterized in that it contains one or more cationic compound (s) of the formula I.
wherein each AO is independently an alkoxy group. R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl or alkenyl groups or -TR ⁵ , R ⁵ = C _5-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- for a Counterions are present 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 based on the weight of the molded body. 21. Detergent tablet according to claim 20, characterized in that it contains the cationi contains (s) compound (s) in release-delayed form. 22. 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% by weight of cationic compounds of the formula I.
  wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl- or -alkenyl groups or -TR ⁵ ; R ⁵ = C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- stand for a counter ion,

consists. 23. Multi-phase detergent tablet according to claim 22, characterized in that the phases have the form of layers and the shaped body is 2-, 3- or 4-phase. 24. Multi-phase detergent tablet according to claim 22, characterized in that it from a base molding which has a cavity and an at least partially in part of the cavity.   25. Multi-phase detergent tablet according to claim 24, 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 wt .-%, preferably 1 to 50 wt .-% and in particular 5 to 40 wt .-% cationic compounds of formula I.
  wherein each AO is independently an alkoxy group, R ^{1 is} selected from -H or C _1-6 alkyl, each group R ² , R ³ , R ^{4 is} independently selected from -H or C _1-28 alkyl - or -alkenyl groups or -TR ⁵ ; R ⁵ C _8-28 alkyl T = -O-CO- or -CO-O-, a, b, c, d, e, f, x, y, z for integers from 0 to 50 and X ^- for stand a counter ion

consists.