WO2001019948A1 - Clear rinsing agent - Google Patents

Abstract

The use of diquaternary polysiloxanes in detergents for machine dishwashing leads to advantageous effects, especially when the diquaternary polysiloxanes are used in the clear rinsing cycle. Diquaternary polysiloxanes of formula (I) are preferably used in which: Z represents a quaternized nitrogen center; R' and R'', independent of one another, represent a C1-C4- alkyl radical or an aryl radical; M represents a bivalent hydrocarbon radical which has at least 4 carbon atoms, which preferably comprises at least one hydroxy group, and which can be interrupted by one or more oxygen atoms and/or groups of the type -C(O)-, -C(O)O- or -C(O)N-; n represents a number ranging from 1 to 201, and; X- represents an inorganic or organic anion.

Description

 .Klarspülmittel '

The present invention relates to the use of diquaternary polysiloxanes in detergents and rinse aids for automatic dishwashing. Rinse aids for machine dishwashing, as well as forms of supply which provide detergents and rinse aids in one product, and the production processes for such rinse aids and detergents are further objects of the present invention.

Today, machine-washed dishes are often subject to higher requirements than hand-washed dishes. For example, dishes that have been completely cleaned of food residues are not considered to be perfect if, after machine dishwashing, they still show whitish stains due to water hardness or other mineral salts, which, due to the lack of wetting agents, come from dried water drops.

To obtain shiny and spotless dishes, rinse aid is used successfully today. The addition of rinse aid at the end of the wash program ensures that the water runs off the dishes as completely as possible, so that the different surfaces are residue-free and immaculately shiny at the end of the wash program.

The automatic cleaning of dishes in household dishwashers usually comprises a pre-wash, a main wash and a rinse cycle, which are interrupted by intermediate wash cycles. In most machines, the pre-wash cycle for heavily soiled dishes can be activated, but is only selected by the consumer in exceptional cases, so that in most machines a main wash cycle, an intermediate wash cycle clean water and a rinse cycle. The temperature of the main wash cycle varies between 40 and 65 ° C depending on the machine type and program level selection. In the rinse cycle, rinse aids are added from a dosing tank in the machine, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is to prevent limescale and deposits on the cleaned dishes. In addition to water and low-foaming nonionic surfactants, these rinse aids often also contain hydrotopes, pH regulators such as citric acid or scale-inhibiting polymers.

Liquid rinse aids are known from EP-Bl 0 197 434 (Henkel), which contain mixed ethers as nonionic surfactants. A variety of different materials (glass, metal, silver, plastic, porcelain) are cleaned in the dishwasher. This variety of materials must be wetted as well as possible in the rinse cycle. Rinse aid formulations which contain only mixed ethers as the surfactant component do not meet these requirements, or do so only to a limited extent, so that the rinse aid or drying effect is unsatisfactory, particularly in the case of plastic surfaces.

The storage tank in the dishwasher must be filled with rinse aid at regular intervals, with one filling sufficient for 10 to 50 rinse cycles, depending on the machine type. If you forget to fill up the tank, glasses in particular become unsightly due to limescale and deposits. In the prior art there are therefore some proposed solutions for integrating a rinse aid into the detergent for machine dishwashing. These proposed solutions are tied to the offer form of the compact molded body.

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

The older German patent application DE 198 51 426.3 (Henkel KGaA) describes a process for the production of multiphase detergent tablets, in which a particulate premix is pressed to give moldings which have a trough, which is subsequently made from a melt suspension or emulsion produced separately Envelope and one or more active substance (s) dispersed or suspended in it.

A form of supply that can be used both separately as solid rinse aid to be dosed by the consumer and as an admixture component for powdered machine dishwashing detergents is described in the older German patent application DE 199 14.364.1 (Henkel KGaA).

The object of the present invention was to provide new rinse aids which deliver at least the same results in terms of application properties as commercially available rinse aids and which also provide further performance advantages. The new rinse aid should be used both as a conventional rinse aid and in the form of combination products and should display its advantageous properties regardless of the form of preparation. Last but not least, the use of the new rinse aid should also be possible in conventional detergents for automatic dishwashing, i.e. the funds should also enable performance benefits as an additional component.

It has now been found that the use of diquaternary polysiloxanes in detergents for automatic dishwashing brings about advantageous effects. It is particularly advantageous if the diquaternary polysiloxanes are used in the rinse cycle.

The present invention therefore relates in a first embodiment to the use of diquaternary polysiloxanes in automatic dishwashing detergents. The mere addition of these compounds to cleaning agents has the effect that the items of crockery treated with such agents become significantly cleaner in subsequent cleaning operations than items of crockery that have been washed with conventional agents. The effect is independent of whether the automatic dishwashing detergents are liquid, powdered or in tablet form.

As an additional positive effect, there is a shortening of the drying time of the dishes treated with the cleaning agent, i.e. the consumer can take the dishes out of the machine and reuse them earlier after the cleaning program has ended.

The invention is characterized by an improved “cleanability” of the treated substrates in later cleaning processes and by a considerable reduction in the drying time compared to comparable agents without the use of diquaternary polysiloxane. In addition to this primary effect according to the invention, the diquaternary polysiloxane unfolds, as expected, that of the silicones Surprisingly, liquid compositions which contain diquaternary polysiloxanes also show not only an unimpaired but usually even increased cleaning ability as well as a consistently increased low-temperature stability due to the diquaternary polysiloxane.

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

Diquaternary polysiloxanes in the context of the invention are polyorganosiloxanes (= silicones) with two quaternized organic ammonium groups, ie two quaternary nitrogen atoms, each carrying four organic radicals and each being bonded to a silicon atom of the polyorganosiloxane via one of these four radicals. According to the invention, diquaternary polysiloxanes are used or used individually or as mixtures of different diquaternary polysiloxanes in the agent or method. It is particularly advantageous. if the diquaternary polysiloxanes are present in the last rinse cycle, ie in the rinse cycle. In this way, the beneficial effect is not weakened by subsequent rinse cycles. Another object of the invention therefore provides for the use of diquaternary polysiloxanes in the rinse cycle in automatic dishwashing.

The diquaternary polysiloxanes used according to the invention are preferably compounds of the formula I

2Θ

R 'R' R 'I Z - M - Si-O-Si-Oτ-Si-M - Z 2 X θ

(I)

I R "R" R "n-1

in the Z a quaternized nitrogen center,

R 'and R "independently of one another

or an aryl radical, M is a divalent hydrocarbon radical with at least 4 carbon atoms, which preferably has at least one hydroxyl group and is substituted by one or more oxygen atoms and / or groups of the type -C (0) -, -C (O) O- or -C (O ) N- can be interrupted, n represents a number from 1 to 201 and X ^"represents an inorganic or organic anion, as described, for example, in DE 37 19 086 Cl and EP 0 294 642 B1.

Diquaternary polysiloxanes used with particular preference are the diquaternary poly (dimethylsiloxanes) of the formula II,

2 X Θ (II)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁹ , R ¹⁰ independently of one another C 22 alkyl or C2-22 alkylene radicals without or with one or more hydroxyl groups or radicals - CH ₂ - Aryl, preferably at least one of the radicals R ¹ , R ² , R ³ having at least 10 carbon atoms or one of the radicals R ¹ , R ² , R ^{3 being} a benzyl radical, R ^{6 being} an oxygen atom or a group -N (R ⁸ ), where R ^{8 is} a C 1 -C 4 -alkyl or hydroxyalkyl radical or hydrogen, M is a divalent hydrocarbon radical with at least 4 carbon atoms, which preferably has at least one hydroxyl group and is substituted by one or more oxygen atoms and / or groups of the type -C (O) -, - C (O) O- or -C (O) N- can be interrupted, n represents a number from 1 to 201 and X ^{~ represents} an inorganic or organic anion.

These are in particular diquaternary poly (dimethylsiloxanes) of the formula III,

in which R is a C _6-22 -alkyl or -alkylene radical, in particular a stearyl radical,

M is a spacer of the formula CH ₂ CH (OH) CH ₂ O (CH ₂ ) ₃ , the connectivity

N ⁺ -M-Si of the spacer N ⁺ -CH ₂ CH (OH) CH ₂ O (CH ₂ ) ₃ -Si corresponds, n is a number from 1 to 100, in particular 10, 30 or 50, and

X ^"represents an inorganic or organic anion, preferably an acetate ion.

In addition to acetations, examples of anions suitable according to the invention are also chloride ions, bromide ions, hydrogen sulfate ions and sulfate ions. The diquaternary poly (dimethylsiloxanes) of the formula III which are particularly preferred according to the invention with stearyl radicals R, acetations X ^' and values for n of 10, 30 and 50 are as Tegopren 6920, Tegopren 6922 and Tegopren ^' 6924 from Th. Goldschmidt AG available.

Further examples of diquaternary polysiloxanes of the formulas I to III which are suitable according to the invention can be found in DE 37 19 086 Cl and EP 0 294 642 B1.

The use according to the invention can be realized in a simple manner by incorporating the substances mentioned into liquid, powdered or tableted cleaning agents or into rinse aid. Automatic dishwashing detergents containing di-quaternized polysiloxanes are also the subject of the present invention.

In preferred embodiments of the present invention, the diquatered polysiloxanes are used in the rinse cycle of automatic dishwashing. Preferred further embodiments of the present invention therefore relate to rinse aids for automatic dishwashing and combination forms which combine detergents and rinse aids, the latter being offered in particular in powder or tablet form.

Another preferred object of the present invention are rinse aids for automatic dishwashing, which contain diquaternary polysiloxanes.

Such rinse aids are - as described above - put 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 capacity of the tank, one tank filling is usually sufficient for 10 to 50 rinsing cycles.

Analogous to the preferred use (see above), rinse aids according to the invention are also preferred which contain one or more diquaternary polysiloxanes of the formula I, 2®

R 'R' R '

I I I Z— M— Si-O- -Si-O- -Si-M— Z 2 X ^ (I)

I I I R "R" R "n-1

in the Z a quaternized nitrogen center,

R 'and R "independently of one another are a C alkyl radical or an aryl radical, M is a divalent hydrocarbon radical with at least 4 carbon atoms, which preferably has at least one hydroxyl group and is substituted by one or more oxygen atoms and / or groups of the type - C (O) -, - C (O) O- or -C (O) N- can be interrupted, n is a number from 1 to 201 and

X ^{~ represents} an inorganic or organic anion, with rinse aids being preferred which contain one or more diquaternary poly (dimethylsiloxanes) of the formula II,

CH, CH, ₂ ® l " ³ I ³ I ³ Z- -SiO- SiO- Si-MZ 2 X Θ (II)

Cr CH. CH, n- l

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁹ , R ¹⁰ independently of one another C ,. ₂ 2-alkyl or C _2-2 2-alkylene radicals without or with one or more hydroxyl groups or radicals -CH2-aryl, preferably at least one of the radicals R ¹ , R ² , R ³ having at least 10 carbon atoms or one of the R, R, R is a benzyl radical, R ^{6 is} an oxygen atom or a group -N (R ⁸ ). where R is a C alkyl or

Is hydroxyalkyl or hydrogen, M is a divalent hydrocarbon radical with at least 4 carbon atoms, which preferably has at least one hydroxy group and one or more Oxygen atoms and / or groups of the type -C (O) -, -C (O) 0— or -C (O) N- can be interrupted, n is a number from 1 to 201 and

X ^"represents an inorganic or organic anion, and those agents are particularly preferred which contain one or more diquaternary

Poly (dimethylsiloxanes) of the formula III,

in which R is a C _6-22 alkyl or alkylene radical, in particular a stearyl radical, M is a spacer of the formula CH ₂ CH (OH) CH ₂ O (CH ₂ ) ₃ , n is a number from 1 to 100, in particular 10, 30 or 50, and X ^"represents an inorganic or organic anion, preferably an acetate ion.

The content of one or more diquaternary polysiloxanes in the agents according to the invention can vary depending on the intended use and the desired product performance, preferred rinse aid according to the invention containing the diquaternary polysiloxane (s) in amounts of 0.001 to 20% by weight, preferably from 0.01 to 10% by weight, particularly preferably from 0.1 to 5% by weight and in particular from 0.15 to 2.5% by weight, in each case based on the rinse aid.

The agents according to the invention can also contain anionic, nonionic, cationic and / or amphoteric surfactants as the surfactant component, nonionic surfactants being preferred due to their foaming power.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C 1 -C ₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates Fonaten and disulfonates, such as those obtained from C _{2-0 8} monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, into consideration. Alkanesulfonates made from

for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 1 -C ₂ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 1 -C 2 -oxoalcohols and those half esters secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. From the washing are the Ci2-Cι ₆ alkyl sulfates and C ₁₂ - C ₅ alkyl sulfates and Cι ₄ -Cι preferably ₅ alkyl sulfates. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _-2 ι alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C ₉ n alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci ₂ -ι ₈ -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- ι ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, 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 fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or taig fatty acids, derived soap mixtures.

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm or tallow fat, are or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol is preferred. The preferred ethoxylated alcohols include, for example, -C ₂ -C ₄ alcohols with 3 EO or 4 EO, C ₉ -C 1 alcohol with 7 EO, C ₁₃ -5. Alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁ -ig alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ - ₁ 4 alcohol with 3 EO and ₂ - ₁ s 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of preferably used nonionic surfactants, which are used 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.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (IV), R ^]

R-CO-N- [Z] (IV)

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 (V)

R ^Ϊ -OR ^

R-CO-N- [Z] (V)

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 is an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C _{] -} alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

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

Low-foaming nonionic surfactants are used as preferred surfactants. The detergent components according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, _2- Cι ι ₄ alcohols containing 3 EO or 4 EO, C n _9- alcohol with 7 EO, Cι ι _3- alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Cι _2- ι ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cι _2- ι ₄ - alcohol with 3 EO and

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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Rinse aids according to the invention which contain a nonionic surfactant which has a melting point above room temperature are particularly preferred. Accordingly, preferred rinse aids are characterized in that they contain nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C. Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such

(PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms _(C16 - ₂₀ - alcohol), preferably a Cig-alcohol and at least 12 moles, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide. Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

Contain Accordingly, particularly preferred rinse aid according to the invention ethoxylated (s) nonionic surfactant (s), which / from C ₆ - ₂ o-monohydroxy alkanols or C ₆ - ₂ o-alkyl phenols or Cι _6-20 fatty alcohols and more than 12 mol, preferably more than 15 moles 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 up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight make up the nonionic surfactant included.

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

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

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 [CH2CH (OH) R ² ],

in which R represents a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ^{2 represents} a linear or branched Designated hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y for a value of at least 15.

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

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

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, ahphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl -, 2-butyl or 2-methyl-2-butyl, 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, ahphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x> 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH) 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 greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa , Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

R ¹ 0 [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 has} 9 to 14 carbon 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

RO [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] jOR ²

contain in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, ahphatic 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 0 [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

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

Instead of the surfactants mentioned or in combination with them, cationic and / or amphoteric surfactants can also be used. In summary, rinse aids according to the invention are preferred, the surfactant (s), preferably nonionic surfactant (s) and in particular nonionic surfactant (s) from the group of the alkoxylated alcohols, in amounts of 0.1 to 40% by weight , preferably from 0.5 to 30% by weight, particularly preferably from 1 to 20 wt .-%, and in particular from 2 to 15 wt .-%, each based on the rinse aid.

Non-aqueous solvents that 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 concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or 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 glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, Propylene glycol t-butyl ether and mixtures of these solvents, so that preferred rinse aids are characterized in that they are non-aqueous solvents, preferably ethanol, n-propanol, i-propanol, 1-butanol, 2-butanol, glycol, propanediol , Butanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butylet forth, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol , Propylene glycol t-butyl ether and mixtures of these solvents.

The rinse aids of the present invention may further contain hydrotropes. The addition of such substances causes a poorly soluble substance to become water-soluble in the presence of the hydrotrope, which is not itself a solvent. Substances that bring about such an improvement in solubility are referred to as hydrotropes or hydrotropes. Typical hydrotropes, for example in the assembly of liquid washing or cleaning agents, are xylene and cumene sulfonate. Other substances, such as urea or N-methylacetamide, increase the solubility through a structure-breaking effect in which the water structure in the vicinity of the hydrophobic group of 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

in which each of the radicals R 1, R ₃ , R ₄ , R is independently selected from H or a C 1 -C 1 -alkyl or -alkenyl radical and X is a cation.

Preferred substituents R 1, R ₂ , R ₃ , R ₄ , R ₅ are selected independently of one another from H or a methyl, ethyl, “-propyl-, where-propyl-,“ -butyl-, where-butyl-, tert - Butyl, «-pentyl, ώo-pentyl or« eo-pentyl radical. As a rule, at least three of the radicals R ¹ to R 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 on each other. In the case of monosubstituted compounds of the formula I, it is preferred if the radical R _{3 is} an alkyl radical, while Ri, R ₂ , R ₄ and R are H (pαrα substitution).

In the context of the present invention, particularly preferred aromatic sulfonates are toluene, cumene or xylene sulfonate.

Of the two industrially available toluenesulfonates (ortho- and /. Αra-toluenesulfonate), the p αrα isomer is preferred in the context of the present invention. The /.αra- isopropylbenzenesulfonate is also the preferred compound in the case of cumene sulfonates. Since xylene is usually used industrially as a mixture of isomers, the technically available xylene sulfonate is also a mixture of several compounds which results from the sulfonation of ortho-, meta- and p αrα-xylene. In these isomer mixtures, the compounds dominate in which the following radicals in the general formula I are thyl groups (all other radicals stand for H): R) and R ₂ , Ri and R, Ri and R and R _\ and R ₅ . In the case of the xylene sulfonates, there is therefore preferably at least one methyl group in the position / zo position relative 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 0.3 to 5% by weight and in particular 0.5 to 3% by weight, based in each case on the rinse aid.

Acidification agents can also be added to the rinse aids according to the invention in order to lower the pH of the liquor in the rinse cycle. Both inorganic acids and organic acids are suitable here as long as they are compatible with the other ingredients. For reasons of consumer protection and handling safety, the solid mono-, oligo- and polycarboxylic acids in particular can be used. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. A commercially available Acidifiziemngsmittel in the present invention also preferably be used is Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid ( max. 33% by weight). Rinse aids which contain acidifying agents, preferably organic acids with particular preference for adipic acid, amidosulfonic acid, succinic acid, citric acid, fumaric acid, maleic acid, malonic acid, oxalic acid and tartaric acid and mixtures of these acids, are preferred embodiments of the present invention.

The rinse aids according to the invention can preferably additionally contain one or more substances from the groups of soil-release polymers, dyes and fragrances. These are described in detail below. The rinse aids described above are suitable for dosing via the storage tank of commercially available dishwashers. The preferred use of the diquaternary polysiloxanes according to the invention can, however, also be achieved by providing dissolution-delayed forms of supply which the consumer doses into the dishwasher before the start of the cleaning cycle, but only release the active ingredients in the rinse cycle. 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, which 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 fatty substances), d) 0 to 50% by weight of further active substances and / or auxiliaries and e) 0.1 to 70% by weight of diquaternary polysiloxanes.

All substances which are solid at room temperature are suitable as carrier substances a). Usually, you will select substances that have an additional effect in the cleaning process, whereby builders are particularly suitable. Preferred carrier material-containing particulate rinse aids include substances from the group of water-soluble detergent and cleaning agent ingredients, preferably carbonates, bicarbonates, sulfates, phosphates and organic oligocarboxylic acids which are solid at room temperature in amounts of 35 to 60% by weight, as carrier materials. preferably from 40 to 55% by weight and in particular from 45 to 50% by weight, in each case 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 the ingredients b) to e). Such components are usually manufactured by shaping a melted NEN mix of ingredients. Rinse aid particles containing carrier material can be obtained, for example, by spraying, spraying or pouring such a melt onto the carrier materials.

The manufacturing processes are described below; There follows a description of the ingredients b) to d), the amounts given relating to rinse aid particles free of carrier material. If carrier material-based particles are to be produced, the information below relates to the composition of the mixture / melt which is applied to the carrier, the proportion of the particle resulting from the proportions of the mixture and carrier material in the particle.

Various requirements are imposed on the coating substances used in the rinse aid particles according to the invention, which on the one hand have the melting or solidification behavior, but on the other hand also the material properties of the coating in the solidified state, i.e. in the rinse aid particle. Since the rinse aid particles are to be permanently protected against environmental influences during transport or storage, the coating substance must have a high stability with respect to the shock loads which occur, for example, during packaging or transport. The coating substance should therefore either have at least partially elastic or at least plastic properties in order to react to an impact load caused by elastic or plastic deformation and not to break. The coating substance should have a melting range (solidification range) in such a temperature range in which the active substances to be coated are not exposed to excessive thermal stress. On the other hand, however, the melting range must be sufficiently high to still provide effective protection for the enclosed active substances at at least a slightly elevated temperature. 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, as usually occurs with pure, crystalline substances, but instead has a melting range that may include 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 occurs within the specified temperature interval and does not indicate the width of the melting range. The width of the melting range is preferably at least 1 ° C., preferably about 2 to about 3 ° C.

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

The waxes are divided into three groups according to their origin: natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan 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, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated requirements with regard to the softening point can also be used as covering materials. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Synthetic waxes made from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, are also suitable is available under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin '90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used as a coating material according to the invention.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-soluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols are found, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main constituent of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The sheath according to the invention coated Feststofϊpartikel may optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co). Fatty acid glycerol esters or fatty acid alkanolamides, but optionally also water-soluble or only slightly water-soluble polyalkylene glycol compounds, can likewise be used at least in part as a component of the casing.

The coating substance contained in the rinse aid particles according to the invention preferably contains the majority of paraffin wax. This means that at least 50% by weight of the total contained substances, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total coating substance) of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred. In a special embodiment of the invention, the total amount of the coating substance used consists exclusively of paraffin wax.

Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that there is no hydrolysis of the waxes in an alkaline detergent environment (as is the case, for example is to be expected with the waxest), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if the melting temperature in the detergent solution drops below this. Such wax residues usually lead to an unsightly appearance on the cleaned surface and should therefore be avoided.

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

The paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally about 10 to about 30 ° C.) is preferably as high as possible. The more solid wax components present in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing proportion of solid wax components, the resilience of the rinse aid particles against impacts or friction on other surfaces increases, 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, opening pores and exposing the active substances to the environmental influences mentioned above.

In addition to paraffin, the coating substance can also contain one or more of the above-mentioned waxes or wax-like substances as the main constituent. In general, the mixture forming the coating substance should be such that the rinse aid particles are at least largely water-insoluble. The solubility in water should not exceed about 10 mg / 1 at a temperature of about 30 ° C. and should preferably be below 5 mg / 1. In any case, however, the coating should have the lowest possible solubility in water, even in water at an elevated temperature, in order to largely avoid a temperature-dependent release of the active substances.

The principle described above serves to delay the release of ingredients at a certain point in the cleaning cycle and can be used particularly advantageously if the main rinse cycle is carried out at a lower temperature (for example 55 ° C.), so that the active substance from the rinse aid particles only in the rinse cycle at a higher level Temperatures (approx. 70 ° C) is released.

Preferred particulate rinse aid contain one or more substances with a melting range of 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, in each case based on the particle weight, preference being given to particulate substances which contain, 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, where 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 cleaning agent components according to the invention can contain one or more fatty substances, preferred cleaning agent components being characterized in that they contain 1 to 60, preferably 5 to 55, particularly preferably 10 to 50 and in particular 20 to 45% by weight of fatty substances as ingredient c) ) contain.

In the context of this application, fatty substances c) are understood to mean liquid to solid substances from the group of fatty alcohols, fatty acids and fatty acid derivatives, in particular the fatty acid esters, at normal temperature (20 ° C.). In the context of the present application, reaction products of fatty alcohols with alkylene oxides and the salts of fatty acids are among the surfactants (see above) and are not fatty substances in the sense of the invention. According to the invention, preferred fatty substances are fatty alcohols and fatty alcohols. Use mixtures, fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or polyols, fatty acid amides, fatty amines etc.

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

Examples of fatty alcohols are the alcohols 1-hexanol (capro alcohol), 1-heptanol (enanthal alcohol), 1-octanol (caprylic alcohol), 1-nonanol (pelargon alcohol), 1-decanol (capric alcohol), 1, which are accessible from native fats and oils -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-l-ol (oleyl alcohol), 9-trans-octadecen-l-ol (emcyl alcohol), 9-cis-octadecen-l, 12-diol (ricinol alcohol), all-cis- 9,12-octadecadien-l-ol (linoleyl alcohol), all-cis-9,12,15-octadecatrien-l-ol (linolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 9-cis-eicosene -l-ol (gadoleyl alcohol), 5,8,11,14-eicosatetraen-l-ol, 1- heneicosanol, 1-docosanol (behenyl alcohol), 1-3-cis-docosen-l-ol (emcyl 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 Ci ₂ -i ₈ alcohols with Ci ₂ -ι ₄ 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 Ci ₆ -i ₈ alcohols prepared by Ziegler ethylene polymerization. Specific examples of alcohols which can be used as component c) are the above-mentioned alcohols and lauryl alcohol, palmityl and stearyl alcohol and mixtures thereof.

Particularly preferred detergent components of the present invention contain, as ingredient c) one or more Cιo- ₃₀ fatty alcohols, preferably Cι _2-24 fatty alcohols, with particular preference from 1 -Hexadecanol, 1 -Octadecanol, 9-cis-octadecene-l-ol, all- cis -9,12-octadecadien-l-ol, all-cis-9,12,15-octadecatrien-l-ol, 1-docosanol and mixtures thereof. Fatty acids can also be used as ingredient c) .These are largely obtained technically from native fats and oils by hydrolysis.While the alkaline saponification carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to break down the fats in glycine and the free fatty acids cleavage Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids that can be used as fatty substances in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (onanthic acid), octanoic acid (caprylic acid), Nonanic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. In the context of the present compound, preference is given to using fatty acids such as dodecanic acid (lauic acid), tetradecanoic acid (mypstic acid), hexadecane acid (palmitic acid), octadecane acid (steanic acid) acid), docosanic acid (behenic acid), tetracosanoic acid (lignocenoic acid), hexacosanic acid (cerotomic acid), tπacotanic acid (meic acid) and the unsaturated species 9c-hexadecenoic acid (palmitolemic acid), 6c-octadecenoic acid (petro) acid, petro-acidic acid (petro) acid, petro-acidic acid (petro) - Octadecensaure (oleic acid), 9t-Octadecensaure (Elaidmsaure), 9c, 12c-Octadecadιensaure (Lmolsaure), 9t, 12t-Octadecadιensaure (Lmolaidmsaure) and 9c, 12c, 15c- Octadecatreinsaure), of course, Marginic acid, nonadecanoic acid, emcasaic acid, elaeostearic acid and arachidonic acid can be used For cost reasons, it is preferred not to use the remote species, but rather technical mixtures of the individual acids, as can be obtained from fat cleavage. Such mixtures are, for example, coscosol fatty acid (approx. 6% by weight C. ₈ , 6% by weight Cio, 48% by weight C ₂ , 18% by weight C, ₄ , 10% by weight C ₆ , 2% by weight C, ₈ , 8% by weight C, 8, 1% by weight Cig), palm kemol fatty acid ( about 4 wt -% C _8, 5 wt -% Cio, 50 wt -% C12, 1 wt -% C _14, 7 weight -% C, _6, 2 wt -% C _{I 8,} 15 wt -% C, ₈ , 1% by weight C, ₈ ), tallow fatty acid (approx. 3% by weight C _{] 4} , 26% by weight C ₆ , 2% by weight C ₆ , 2% by weight Cπ, 17% by weight Cig, 44% by weight % Cι ₈ , 3 wt -% C _{] 8} , 1 Gew -% Cι ₈ ), hardened tallow fatty acid (approx. 2 Gew -% C _H , 28 Gew -% C _{] 6} , 2 Gew -% C _{] 7} , 63 Gew - % C, ₈ , 1% by weight cig), technical oleic acid (approx. 1% by weight Cι ₂ , 3% by weight C _{) 4} , 5% by weight C, ₆ , 6% by weight C, ₆ , 1% by weight % Cπ, 2% - Cι ₈ , 70% by weight, Cι ₈ , 10% -% Cig, 0.5% -% C, ₈ ), technical palmite / stearic acid (approx. 1% -% Cι ₂ , 2% by weight of C _] , 45% by weight of C ₆ , 2% by weight of C ₎ 7.47 % By weight cig, 1% by weight Cι ₈ ) and soybean oil fatty acid (approx. 2% by weight Cι ₄ , 15% by weight Ciβ, 5% by weight Cig, 25% by weight Cι ₈ -, 45 wt% C, ₈ -, 7 wt% C, ₈ -).

The esters of fatty acids with alkanols, diols or polyols can be used as fatty acid esters, fatty acid polyol esters being preferred. Suitable fatty acid polyol esters are monoesters and diesters of fatty acids with certain polyols. The fatty acids which are esterified with the polyols are preferably saturated or unsaturated fatty acids having 12 to 18 carbon atoms, for example lauric acid, myristic acid, palmitic acid or stearic acid, preference being given to using the technically obtained mixtures of the fatty acids, for example those of coconut -, palm kernel or taig fat derived acid mixtures. In particular, acids or mixtures of acids with 16 to 18 carbon atoms, such as, for example, tallow fatty acid, are suitable for esterification with the polyhydric alcohols. In the context of the present invention, sorbitol, trimethylolpropane, neopentyl glycol, ethylene glycol, polyethylene glycols, glycerol and polyglycerols are suitable as polyols which are esterified with the abovementioned fatty acids.

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

The particulate rinse aid according to the invention can preferably contain, as ingredient d), further active ingredients and / or auxiliaries from the groups of surfactants, bleaching agents, bleach activators, soil-release polymers, enzymes, silver preservatives, complexing agents, dyes and fragrances in amounts of 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 preferred particulate rinse aids are characterized in that they additionally contain 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 15 to 42.5% by weight and in particular 20 to 40% by weight, in each case based on the particulate rinse aid.

The further detergent ingredients that can be incorporated as component d) in the rinse aid according to the invention are described in detail below.

The particulate rinse aid according to the invention contains diquaternary polysiloxanes as ingredient e), the statements made above relating to preferred species being completely analogous. In order to avoid redundancies, reference is made to the formulas mentioned above. Preferred particulate rinse aids contain diquaternary polysiloxanes, preferably diquaternary polysiloxanes of the formula I, particularly preferably diquaternary poly (dimethylsiloxanes) of the formula II and in particular diquaternary poly (dimethylsiloxanes) of the formula III in amounts of 0.5 to 60% by weight, preferably from 1 to 50% by weight, particularly preferably from 2.5 to 40% by weight and in particular from 5 to 30% by weight, in each case based on the particulate rinse aid.

Another object of the present invention is a process for the production of particulate detergent components, which is characterized in that a melt of a) 30 to 70 wt .-% shell substance (s) with a melting point above 50 ° C, b) 0 to 65% by weight of fatty substances), c) 0 to 50% by weight of further active ingredients and / or auxiliaries and d) 0.1 to 70% by weight of diquaternary polysiloxanes are applied to one or more carrier materials and the mixture is shaped. In this variant of the method, a melt is first produced which can contain further active ingredients and auxiliaries. This is placed on a carrier material and processed to give a shape in a mixture with this carrier material.

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

The melt can be applied to the carrier material in all customary mixing devices. The shaping processing step for the mixture of melt and carrier material is likewise not subject to any procedural restrictions, so that the person skilled in the art can also select from the processes familiar to him. In tests by the applicant, methods have been found to be preferred in which the shaping processing is carried out by granulating, compacting, pelletizing, extinguishing or tableting.

The process according to the invention comprises the application of melts from the ingredients a) to d) to carrier materials. In principle, the melt and carrier (s) can be present in varying amounts in the resulting rinse aid particles. Preferred processes are characterized in that a mixture of 5 to 50% by weight, preferably 10 to 45% by weight, particularly preferably 15 to 40% by weight and in particular 20 to 35% by weight of a melt of the ingredients a) to d) and 50 to 95% by weight, preferably 55 to 90% by weight, particularly preferably 60 to 85% by weight and in particular 65 to 80% by weight of carrier material (s) is shaped.

With regard to the ingredients that are used in the method according to the invention and processed into the carrier material-based cleaning agent components according to the invention, what has been said above applies analogously.

The detergent components according to the invention can also be formulated without carrier material, so that they consist only of the ingredients a) to d). For manufacturing The provision of particulate detergent components according to the invention, in particular the prilling, the pastilling and the scaling by means of chill rolls have proven successful.

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 from a) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C., b) 0 to 65% by weight of fatty substances), c) 0 to 50% by weight of further active substances and / or auxiliaries and d) 0.1 to 70% by weight of diquaternary polysiloxanes are injected into a cold gas stream.

The method according to the invention, which is briefly referred to as prilling, comprises the production of granular bodies from meltable substances, the melt from the ingredients a) to d) being sprayed onto the top of a tower in a defined droplet size, solidifying in free fall and the prills on Bottom of the tower accumulate as granules.

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

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

An alternative method of twisting is pastilling. A further embodiment of the present invention therefore provides a process for the production of pastilized detergent components, in which a melt is made from a) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C., b) 0 up to 65% by weight of fatty substances), c) 0 to 50% by weight of further active ingredients and / or auxiliaries and d) 0.1 to 70% by weight of diquaternary polysiloxanes metered onto cooled pastille plates.

Pastilling, which is sometimes also referred to as pelleting, comprises metering the melt from the ingredients a) to d) onto rotating, inclined plates which have a temperature below the melting temperature of the melt and are preferably cooled below room temperature. Here, too, process variants can be carried out in which the pastilles are frozen. However, measures must be taken to prevent the condensation of air humidity.

The pastillation provides larger particles which have sizes between 2 and 10 mm, preferably between 3 and 6 mm, in technically customary processes.

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 process for the production of particulate detergent components, in which a melt from a) 30 to 70 wt .-% of coating substance (s) with a melting point above 50 ° C, b) 0 to 65 wt. % Fatty substances), c) 0 to 50% by weight of further active substances and / or auxiliaries, and d) 0.1 to 70% by weight of diquaternary polysiloxanes are applied or sprayed onto a cooling roll, the solidified melt is scraped off and, if necessary, comminuted ,

The use of cooling rollers enables the desired particle size range to be set without problems, which can also be less than 1 mm, for example 200 to 700 μm, in this method according to the invention.

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

Another object of the present invention is therefore also a particulate machine dishwashing detergent, containing builders and optionally further ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, colorants and fragrances, which comprises a particulate rinse aid according to the invention in quantities from 0.5 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 the total agent.

The ingredients of automatic dishwashing detergents are described below. Some of these can also be contained as active substances or carrier materials in the rinse aid particles according to the invention.

The most important ingredients of machine dishwashing detergents are builders. The detergents for machine dishwashing according to the invention can contain all builders usually used in detergents and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological concerns about their use - also the phosphates. The builders mentioned below are all suitable as carrier materials for the rinse aid particles according to the invention, as has already been explained above.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x θ2 _{X +} ι Η 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. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. 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 θ ₅ ^' yH ₂ O are preferred, with β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The release delay compared to conventional amorphous sodium silicates can have been found in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nra, 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 release delay compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X) , which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

n Na ₂ O ^• (ln) 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 is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ θ ₇ ) at 200 ° C, and at higher temperatures in sodium trimetaphosphate (Na ₃ P ₃ O) 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 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HP0 ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like ^"3 , water loss at 95 °), 7 mol. (Density 1.68 like ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water (density 1.52 like ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes into the diphosphate Na ^ O-? When heated more. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with sodium carbonate solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or Dibasic potassium phosphate), K 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 like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ θ ₅ ) a density of 2.536 like ^"3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction Heating of 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 θ ₇ , exists in anhydrous form (density 2.534 gcm ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ θ 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 ^"3 , which is soluble in water, the pH of which is 1% Solution at 25 ° is 10.4. Condensation of NaH PO ₄ or KH PO produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ Oιo (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O - Well with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ Oιo (potassium tripolyphosphate), comes for example in the form of a 50% by weight solution (> 23% P ₂ O ₅ , 25% KO). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

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

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention. Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of a acid component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

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

In the context 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 carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

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

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,

Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures 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, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 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 a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 owns. Both maltodextrins with a DE between 3 and 20 and dry glucose simpes 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 can be used.

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

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminisisuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol are also preferred in this context. cerintrisuccinate. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

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

In addition to the builders, substances from the groups of surfactants (see above), bleaching agents, bleach activators, enzymes, polymers and colorants and fragrances are particularly important ingredients of cleaning agents. Important representatives from the substance classes mentioned are described below.

Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and supply water in HO. Further 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, phthaloiminoperacid 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 dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, examples of which include alkylperoxyacids and arylperoxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidanoic acid paprooxyacrylic acid , o-

Carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) ahphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxyboxyphthanoic acid, liperiperidic acid, diper , N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in the cleaning agents according to the invention for machine dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleaches mentioned can also be introduced wholly or in part via the rinse aid particles according to the invention into the automatic dishwashing detergents according to the invention in order to achieve "post-bleaching" in the rinse cycle.

Bleach activators that support the effect of the bleaching agents have already been mentioned above as a possible ingredient of the rinse aid particles. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine DADHT and isatoic anhydride ISA.

Compounds which, under perhydrolysis conditions, give ahphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used as bleach activators. Substances which carry 0- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acyherized triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, especially triacetin, 5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or mixtures thereof (SORMAN ), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated s glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used.

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

Bleach activators from the group of multi-acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (N-) or iso-isoblene (N-) iso , n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6 wt .-% based on the total agent used.

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

Suitable enzymes in the cleaning agents according to the invention are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch. Oxidoreductases can also be used for bleaching. Particularly well suited are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Here are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or of protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. 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 coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.

Dyes and fragrances can be added to the automatic dishwashing detergents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensorially "typical and unmistakable" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl benzylatepylpropylate, stylate propylate styrene. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones, for example, the ionones, α -Isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include tephenols such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources, for example Pine, citms, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries. Incorporation of the fragrances into the rinse aid articles according to the invention is also possible and leads to a fragrance impression when the machine is opened (see above).

In order to improve the aesthetic impression of the agents produced according to the invention, it (or parts thereof) can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a long shelf life and are not sensitive to the other ingredients of the compositions and to light, and have no pronounced substantivity to the substrates to be treated with the compositions, such as glass, ceramic or plastic dishes, so as not to stain them.

The cleaning agents according to the invention can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being of particular importance in the field of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, ammotriazoles, alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkyl laminotriazole are particularly preferably to be used. In addition, detergent formulations often contain active chlorine-containing agents that can significantly reduce the corrosion of the silver surface. In chlorine-free cleaners, oxygen and nitrogen-containing organic redox ve compounds such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr. Hf, V, Co and Ce are often used. Preferred here are the transition metal salts selected from the group consisting of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) 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 composition of the rinse aid articles according to the invention is such that they do not dissolve in the main rinse cycle (and also in optional pre-rinse cycles) or only to a minor extent. This ensures that the active substances are only released in the rinse cycle and develop their effect here. In addition to this chemical assembly, depending on the type of dishwasher, physical assembly is required so that the rinse aid items are not pumped out when the water is changed in the machine and are therefore no longer available for the rinse aid. Standard household dishwashers contain a sieve insert in front of the drain pump, which pumps the water or cleaning solution out of the machine after the individual cleaning cycles, which is intended to prevent the pump from becoming blocked by dirt residues. If heavily contaminated crockery is washed by the consumer, this sieve insert must be cleaned regularly, which is easily possible due to the easy accessibility and removability. The size and shape of the rinse aid articles according to the invention are now preferably designed such that they do not pass through the sieve insert of the dishwasher even after the cleaning cycle, ie after exposure to movement in the machine and the cleaning solution. In this way it is ensured that there are rinse aid articles in the dishwasher in the rinse cycle, which release the active substance (s) under the action of the warmer water and bring the desired rinse aid effect. Particulate machine dishwashing agents preferred in the context of the present invention are characterized in that the particulate rinse aid has particle sizes between 1 and 40 mm, preferably between 1.5 and 30 mm and in particular between 2 and 20 mm.

In the dishwashing detergents according to the invention, the rinse aid articles with the above-mentioned sizes can protrude from the matrix of the other particulate ingredients, but the other particles can also have sizes that lie in the range mentioned, so that overall a cleaning agent is formulated that consists of large detergent and Rinse aid article exists. In particular, if the rinse aid articles according to the invention are colored, for example thus have a red, blue, green or yellow color, it is important for the appearance of the product, i.e. of the entire cleaning agent is advantageous if the rinse aid particles are visibly larger than the matrix of the particles of the other ingredients of the cleaning agent. Particulate machine dishwashing detergents according to the invention which have particle sizes between 100 and 3000 μm, preferably between 300 and 2500 μm and in particular between 400 and 2000 μm (without taking into account the rinse aid particles) are preferred here.

In addition to the coloring of the rinse aid particles, the optical attraction of such compositions can also be increased by contrasting coloring of the powder matrix or by the shape of the rinse aid particles. Since technically uncomplicated processes can be used to manufacture the rinse aid articles, it is possible to offer them in a wide variety of forms without any problems. In addition to the particle shape, which has an approximately spherical shape, cylindrical or cube-shaped particles, for example, can be produced and used. Other geometric shapes can also be realized. Special product designs can contain, for example, star-shaped rinse aid articles. Disks or shapes which show plants and animal bodies, for example tree, flower, blossom, sheep, fish, etc., as base area can also be produced without problems. Interesting visual incentives can also be created in this way by producing the rinse aid articles in the form of a stylized glass in order to visually underline the rinse aid effect in the product. There are no limits to your imagination. If the cleaning agents according to the invention are formulated as a powder mixture, partial segregation can occur on the one hand when the package is shaken, in particular when the sizes of rinse aid particles and cleaning agent matrix are very different, on the other hand the dosage can be different in two successive cleaning cycles, since the consumer is not always mandatory dosed the same amount of detergent and rinse aid article. If it is desired to technically always use the same amount per cleaning cycle, this can be achieved by packaging the agents according to the invention in bags made of water-soluble film, which is familiar to the person skilled in the art. The present invention also relates to particulate machine dishwashing detergents in which a dosing unit is welded into a bag made of water-soluble film.

As a result, the consumer only has to insert a bag, which contains, for example, a detergent powder and several optically protruding rinse aid articles, into the dosing compartment of his dishwasher. This embodiment of the present invention is therefore an optically attractive alternative to conventional detergent tablets.

The cleaning agents according to the invention can be produced in a manner known per se. A method of producing powdered machine dishwashing detergent with rinse aid effect, in which a powdered machine dishwashing agent known per se is mixed with rinse aid particles according to the invention, is therefore a further subject of the present invention.

The desired retention of the rinse aid articles in the machine described above, even when changing water, can be achieved in addition to the above-mentioned enlargement of the rinse aid articles by reducing the holes in the sieve insert. In this way, machine dishwashing detergents can be formulated which have a uniform mean particle size which is smaller than, for example, 4 to 12 mm. For this purpose, a sieve insert is added to the product according to the invention, in which the rinse aid articles also have smaller particle sizes, which replaces or covers the insert located in the machine. Another object of the present invention fertilizer is therefore a kit-of-parts, which comprises a powdered dishwasher detergent according to the invention and a sieve insert for domestic dishwashers.

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

The mesh size or hole size should not be too small to prevent the enclosed sieve insert from becoming blocked by dirt residues. Here kits-of-parts according to the invention are preferred, in which the mesh size or hole size of the sieve insert is 1 to 4 mm and the rinse aid articles are larger than this mesh size or hole size of the sieve insert.

The kit-of-parts according to the invention is not limited to the specific shape of the sieve insert in which it replaces or covers the insert located in the machine. According to the invention, it is also possible and preferred to include a sieve insert in the kit-of-parts which has the shape of a basket which can be hung in the dishwasher - for example on the cutlery basket - in a known manner. In this way, a sieve insert designed in this way replaces the dosing chamber, i.e. the consumer doses the automatic dishwashing agent according to the invention directly into this sieve insert, which acts in the cleaning and rinse cycle in the manner described above.

The advantages according to the invention can also be used in the form of the compact molded body. Another object of the present invention is therefore also a shaped detergent for machine dishwashing, containing builders and optionally further ingredients of detergents, the diquaternary polysiloxanes, preferably diquaternary polysiloxanes of the formula I, particularly preferably diquaternary poly (dimethylsiloxanes) of the formula II and in particular diquaternary Po - ly (dimethylsiloxanes) of the formula III 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 molded body weight, contains.

Here, too, reference can be made to the above information with regard to preferred embodiments. As already mentioned, the introduction of the diquaternary polysiloxanes into the rinse aid is particularly preferred, so that preferred detergent tablets are characterized in that they contain the diquaternary polysiloxanes in a solution-delayed form.

Not only is a release delay particularly preferred here, but a controlled release which does not aim at slower solubility but at release controlled by external circumstances. The rinse aid articles described above can also be formulated as molded bodies and also offer the possibility of temperature-controlled release of the diquaternary polysiloxanes in molded bodies.

The present invention therefore furthermore relates to multi-phase detergent tablets for machine dishwashing, containing builders and, optionally, further detergent ingredients in which at least one phase consists of a) 0 to 65% by weight of one or more carrier materials, b) 30 to 70% by weight .-% enveloping substance (s) with a melting point above 50 ° C, c) 0 to 65 wt .-% fat), d) 0 to 50 wt .-% of other active substances and / or auxiliaries and e) 0.1 up to 70 wt .-% diquaternary polysiloxanes.

Completely analogous to the above statements regarding the particulate rinse aid, the same embodiments (amount, type and packaging of the ingredients, etc.) are also preferred for the molded articles according to the invention.

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

The shaped bodies according to the invention can take on any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, five, ellipsoid hexagonal and octagonal prismatic and rhombohedral shapes are preferred. Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the shaped bodies according to the invention have corners and edges, they are preferably capped. As an additional optical differentiation, an embodiment with chamfered corners and chamfered ("chamfered") edges is preferred.

Instead of the layer structure, molded bodies can also be produced which contain the detergent component according to the invention in the form of other phases. It has proven useful here to produce basic molded articles which have one or more cavities and to fill the melt from the constituents a) to d) of the detergent component according to the invention into the cavity and to solidify it there. This manufacturing process results in preferred multi-phase detergent molded articles which consist of a basic molded article which has a cavity and an at least partially contained part of the cavity.

The cavity in the molded part of such molded bodies according to the invention can have any shape. It can cut through the molded body, ie an opening at different which have sides, for example on the top and bottom of the molded body, but it can also be a cavity which does not extend through the entire molded body and whose opening is only visible on one side of the molded body. The shape of the cavity can also be freely selected within wide limits. For reasons of process economy, through holes, the openings of which lie on opposite surfaces of the molded body, and troughs with an opening on one side of the molded body have proven successful. In preferred detergent and cleaning agent bodies, the cavity is in the form of a through hole, the openings of which are located on two opposing surfaces of the body. The shape of such a through hole can be chosen freely, with preference being given to shaped bodies in which the through hole has circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, hexagonal or octagonal horizontal sections. Completely irregular hole shapes such as arrow or animal shapes, trees, clouds etc. can also be realized. As with the molded bodies, in the case of square holes, those with chamfered corners and edges or with rounded corners and chamfered edges are preferred.

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

If the above-mentioned principle of the hole open on two opposite sides of the shaped body is reduced to one opening, trough shaped bodies are obtained. Detergent shaped articles according to the invention, in which the cavity has the shape of a depression, are likewise preferred. As with the “perforated bodies”, the shaped bodies according to the invention can also assume any geometric shape in this embodiment, in particular concave, convex, biconcave, biconvex, cubic, tetrahedral gonal, orthorhombic, cylindrical, spherical, cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, seven- and octagonal-prismatic and rhombohedral shapes are preferred. Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the molded body has corners and edges, these are preferably capped. As an additional optical differentiation, an embodiment with rounded corners and beveled (“chamfered”) edges is preferred.

The shape of the trough can also be chosen freely, preference being given to shaped bodies in which at least one trough has a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid , five, seven and octagonal prismatic and rhombohedral shape can take. Completely irregular trough shapes such as arrow or animal shapes, trees, clouds, etc. can also be realized. As with the molded bodies, troughs with chamfered corners and edges or with chamfered corners and chamfered edges are 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, multi-phase detergent tablets are preferred, in which the part contained in the cavity from 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> 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 fatty substances), d) 0 to 50% by weight, preferably 5 to 45% by weight and in particular 10 to 40% by weight of further active ingredients and / or auxiliaries and e) 0.1 to 70% by weight, preferably 1 to 50% by weight and in particular 5 to 40% by weight of diquaternary polysiloxanes consists.

The size of the trough or the through hole in comparison to the entire molded body depends on the intended use of the molded body. The size of the cavity can vary depending on how much more active substance the remaining hollow volume is to be filled with and whether a smaller or larger amount of detergent component is to be contained. Regardless of the intended use, detergent tablets are preferred in which the volume ratio of the pressed part (“basic tablet”) to the detergent component is 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, the two values correlating with one another via the densities of the basic molded body or the detergent component. Regardless of the density of the individual parts, detergent tablets according to the invention are preferred in which the weight ratio of basic molded article to detergent component is 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and is in particular 4: 1 to 30: 1.

Analogous information can also be given for the surfaces that are visible from the basic molded body or from the detergent component. Here, detergent tablets are preferred in which the outwardly visible surface of the detergent component makes up 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 article

The detergent component and the basic molded body are preferably colored to be optically distinguishable. In addition to the optical differentiation, application-related advantages can be achieved through different solubilities of the different shaped body areas. Detergent molded articles in which the detergent component dissolves faster than the basic molded article are preferred according to the invention. By incoφoration of certain components, on the one hand, the solubility of the detergent component can be specifically accelerated, on the other hand, the release of certain ingredients from the detergent component can be advantageous in washing or Carry out cleaning process.

Of course, detergent tablets according to the invention are also preferred, in which the detergent component dissolves later in the washing program than the basic tablet. Performance advantages from this delayed release can be achieved, for example, by using a slow-release detergent component to release active substance (s) only in later rinses. In machine dishwashing, for example, detergent components which dissolve more slowly can result in additional active substance (s) being available in the rinse cycle. Additional substances such as non-ionic surfactants, acidifiers, soil-release polymers, etc. can be used to improve the rinse aid results. Incorporation of perfume is also possible without any problems; the delayed release in dishwashers can eliminate the “lye odor” that often occurs when the machine is opened. The ingredients acidifying agents, soil release polymers, etc., based on the detergent components according to the invention, are then ingredients d).

In preferred embodiments of the present invention, the basic molded body has a high specific weight. Detergent shaped bodies, which are characterized in that the basic shaped body has a density above 1000 kgdm ^" , preferably above 1025 kgdm ^" , 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 incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or disintegration accelerators are understood to be auxiliaries which are quick to use Disintegration of tablets in water or gastric juice and release of the pharmaceuticals in an absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used, swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or Casein derivatives.

Preferred detergent molded articles 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 based on the molded article weight. If only the basic molded article contains disintegration aids, the information given relates only to the weight of the basic molded article. When disintegration aids are incoφorated in the detergent components according to the invention, those count as ingredients d).

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight .-% contain. Pure cellulose has the formal composition (C ₆ Hι ₀ O ₅ ) _n and, formally speaking, is a ß-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 Verestemngen or Verethemngen in which hydroxy hydrogen atoms were substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom can also be used as cellulose derivatives. The category of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. Detergent tablets, which contain disintegrants in granular or optionally granulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A Subsequent disaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of approximately 5 μm and can be compacted, for example, to granules with an average particle size of 200 μm.

Preferred detergent tablets in the context of the present invention additionally contain 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 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the molded body.

The detergent tablets according to the invention can also contain a gas-developing shower system both in the base tablet and in the detergent component. The gas-developing shower system can consist of a single substance that releases a gas when it comes into contact with water. Among these compounds, magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water. Usually, however, the gas-releasing nozzle system in turn consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and feasible here, which release nitrogen, oxygen or hydrogen, for example, the mistletoe system used in the detergent shaped body according to the invention can be selected on the basis of both economic and ecological considerations. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and bicarbonates may be preferred for reasons of washing technology. In preferred shaped detergent bodies, 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3, are used as the effervescent system up to 10% by weight of an acidifying agent, based in each case on the entire molded body.

Acidification agents which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. For this group, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred. Organic sulfonic acids such as amidosulfonic acid can also be used. A commercially available Acidifiziemngsmittel in the present invention also preferably be used is Sokalan ^® DCS (trademark of 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 shaped detergent bodies in which a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures of these are used as acidifying agents in the shower system.

The particulate detergents and / or detergent tablets can - like the detergent components according to the invention - be packaged after manufacture, the use of certain packing 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) shaped detergent or cleaning article (s) according to the invention and one containing the cleaning agent and / or the washing and cleaning agent shaped article Packaging system, the packaging system having a moisture vapor transmission rate of 0.1 g / m / day to less than 20 g / m / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

The packaging system of the combination of cleaning agent component and / or cleaning agent and / or washing and cleaning agent shaped body (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 that Packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. The specified temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being sealed at the top with the material to be tested. The moisture vapor permeability rate can be determined from the surface of the container which is sealed with the material to be tested (permeation surface), the weight increase in calcium chloride and the exposure time

calculate, where A is the area of the material to be tested in cm ", 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 air humidity”, is 85% when measuring the moisture vapor transmission rate in the context of the present invention at 23 ° C. The air absorption capacity for water vapor increases with the temperature up to a respective maximum content, the so-called saturation level - stop, and is given in g / m. For example, 1 πr air of 17 ° is saturated with 14.4 g of water vapor; at a temperature of 11 ° there is saturation with just 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 ^" water vapor, then the relative humidity = (12 / 14.4) -100 = 83%. If this air is cooled, then the saturation (100% r.L.) reached at the so-called dew point (in the example: 14 °), ie if it cools further, a precipitate is formed in the form of fog (dew). Hygrometers and psychometers are used to quantify the moisture.

The relative equilibrium humidity of 85% at 23 ° C can be adjusted to +/- 2% r.L. in laboratory chambers with humidity control, for example, depending on the device type. adjust exactly. Even over saturated solutions of certain salts, constant and well-defined relative air humidities form in closed systems at a given temperature, which strive for the phase equilibrium between partial pressure of the water, saturated solution and soil body.

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

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

Depending on the embodiment of the invention, the packaging system of the combination according to the invention includes a certain amount of detergent component according to the invention, a certain amount of a particulate detergent composition or one or more detergent tablets. It is preferred according to the invention to either design a shaped body such that it comprises an application unit of the detergent and cleaning agent, and this shaped body to be packed individually, or to pack the number of molded articles into one packaging unit, which in total comprises one application unit. With a SoUdosiemng of 80 g of detergents and cleaning agents, it is therefore possible according to the invention to produce and individually pack an 80 g heavy detergent and cleaning product, but it is also possible according to the invention to pack two 40 g heavy detergents in one package to arrive at a combination according to the invention. This principle can of course be expanded, so that combinations according to the invention can also contain three, four, five or even more detergent tablets in one packaging unit. Of course, two or more molded bodies in a packaging can have different compositions. In this way it is possible to spatially separate certain components from one another, for example in order to avoid stability problems.

The packaging system of the combination according to the invention can consist of a wide variety of materials and can take on any external shape. For economic reasons and for reasons of easier processability, however, packaging systems are preferred in which the packaging material is light in weight, easy to process and inexpensive. In combinations preferred according to the invention, the packaging system consists of a sack or pouch made of single-layer or laminated paper and / or plastic film.

The detergent tablets can be unsorted, that is, as a loose fill, filled into a bag made of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferred to fill the detergent and cleaning product tablets individually or in groups in sacks or bags. For individual application units of the detergent tablets that are in a sack or bag, the term "flow pack" has become common in the art. Such "flow packs" can then - again preferably sorted - optionally be packed in repackaging, whatever the compact offer form 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 sealed by heat (hot fusion), adhesives or adhesive tapes become. Single-layer bag or sack materials are the known papers, which can optionally be impregnated, and plastic films, which can optionally be co-extruded. Plastic films which can be used as a packaging system in the context of the present invention are given, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193. Figure 111 shown there gives at the same time Indications of the water vapor permeability of the materials mentioned.

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

Although it is possible to use wax-coated papers in the form of cardboard boxes as packaging systems for the detergent tablets, in addition to the films or papers mentioned, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax-coated paper. The term “packaging system” in the context of the present invention always denotes the primary packaging of the detergent component, detergent composition or molded article, i.e. the packaging that is in direct contact with the detergent component, detergent composition or molded body surface on the inside. No requirements are placed on an optional secondary packaging, so that all common materials and systems can be used here.

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

The relative equilibrium moisture content of the detergents or detergent shaped bodies can be determined by conventional methods, the following procedure being chosen in the course of the present investigations: A water-impermeable 1-liter container with a lid, which has a closable opening for capturing Samples, was filled with a total of 300 g of detergent and cleaning agent mold and kept at a constant 23 ° C for 24 h to ensure a uniform temperature of the vessel and substance. The water vapor pressure in the space above the molded body can then be determined with a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now measured every 10 minutes until two successive values show no deviation (equilibrium moisture). The above Hygrometer allows a direct display of the recorded values in% relative humidity.

Also preferred are embodiments of the combination according to the invention in which the packaging system is designed to be resealable. Combinations in which the packaging system has a microperforation can also be preferably implemented according to the invention.

As mentioned above, detergent components, detergent compositions or detergent tablets for automatic dishwashing can be produced by the methods according to the invention. Accordingly, a cleaning process for cleaning dishes in a dishwasher is characterized in that one or more particle-shaped cleaning agents according to the invention and or one or more washing or cleaning agent tablets according to the invention are inserted into the dosing chamber of the dishwasher and a rinsing program can run, in the course of which the dosing chamber opens and the cleaning agent or agents and or the or the shaped body are resolved, another object of the present invention.

The dosing chamber can also be dispensed with in the cleaning method according to the invention and the cleaning agent components or cleaning agent compositions according to the invention or the molded article (s) according to the invention can be inserted, for example, into the cutlery basket. Of course, the use of a dosing aid, for example a basket, which is attached to the wash cabinet, is also possible without any problems. Accordingly, a cleaning method for cleaning dishes in a dishwasher is characterized in that one or more particulate detergents according to the invention and / or one or more detergent tablets according to the invention with or without dosing aid are added to the washing machine Inserting the washing compartment of the dishwasher and running a washing program, in the course of which the cleaning agent (s) and / or the molding (s) are dissolved, is another object of the present invention.

Examples:

Dishes soiled with standard soiling (see below) were washed with a commercially available machine dishwashing detergent in powder form (dosage: 25 g), a comparative example V being used to add a commercially available rinse aid from the machine's storage tank. In Inventive Example E of the commercially available rinse aid of the comparative example prior to use by addition of Tegopren ^® 6922 (diquatemäres poly (dimethylsiloxanes) of the formula III with stearyl R, acetate ion X ^~ and a value for n of 30, from Th. Goldschmidt AG.) Was upgraded. The metered amount of the rinsing aid amount in both cases 5 ml per rinse cycle, in Inventive Example E was introduced into the rinse cycle ^® 6922 by the Klarspülerdosiemng 1 gram Tegopren. A Miele G 590 with a universal program was used as the dishwasher, the water hardness was 16 ° d.

The dishes washed in this way were again soiled with standard soiling and rinsed again under the conditions described above. The cleaning performance of the rinsing processes was then assessed using the evaluation scale described below. The results of this evaluation are shown in the table below.

The standard soiling was applied according to a standard procedure which is described in "Methods for determining the cleaning performance of machine dishwashing detergents" (part A: SÖFW-Journal, 124th year 11/98, pages 706 to 713; Part B: SÖFW-Journal, 124. Volume 14/98, pages 1022 to 1034) also discloses the evaluation criteria according to which the evaluations listed in the table above were carried out.

The table clearly shows that the dishes treated according to the invention can be cleaned much better in later cleaning cycles than the dishes of the comparative example.

Claims

claims:

1. Use of diquaternary polysiloxanes in automatic dishwashing detergents.

2. Use of diquaternary polysiloxanes in the rinse aid in automatic dishwashing.

3. Use according to one of claims 1 or 2, characterized in that one or more diquaternary polysiloxanes of the formula I,

2®

2 X θ

(I)

in the Z a quaternized nitrogen centimeter,

R 'and R "independently of one another are a C 1 -C 4 -alkyl radical or an aryl radical, M is a divalent hydrocarbon radical with at least 4 carbon atoms, which preferably has at least one hydroxyl group and is substituted by one or more oxygen atoms and / or groups of the type - C (O) - , -C (O) 0- or -C (0) N- can be interrupted, n is a number from 1 to 201 and

X ^"represents an inorganic or organic anion can be used.

4. Use according to one of claims 1 to 3, characterized in that one or more diquaternary poly (dimethylsiloxanes) of the formula II,

Z-M-. 2 X Θ (II)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁹ , R ¹⁰ independently of one another C ₁ . ₂₂ - alkyl or C _2- 22 alkylene radicals without or with one or more hydroxyl groups or radicals -CH ₂ -aryl, preferably at least one of the radicals R ¹ , R ² , R ³ having at least 10 carbon atoms or one of the radicals R ¹ , R ² , R ^{3 is} a benzyl radical,

R em oxygen atom or a group -N (R), where R represents a Cμ- alkyl or hydroxyalkyl radical or hydrogen,

M is a divalent hydrocarbon radical with at least 4 carbon atoms, which preferably has at least one hydroxyl group and is interrupted by one or more oxygen atoms and or groups of the type - C (0) -, -C (O) O- or -C (O) N- can, n be a number from 1 to 201 and

X ^{~ represents} an inorganic or organic anion can be used.

5. Use according to one of claims 1 to 4, characterized in that one or more diquaternary poly (dimethylsiloxanes) of the formula III,

in which R is a C _6-22 alkyl or alkylene radical, in particular a stearyl radical, M is a spacer of the formula CH ₂ CH (OH) CH ₂ O (CH ₂ ) ₃ , n is a number from 1 to 100, in particular 10, 30 or 50, and X ^{~ represents} an inorganic or organic anion, preferably an acetate ion, be used.

6. Rinse aid for automatic dishwashing, containing diquaternary polysiloxanes.

7. rinse aid according to spoke 6, characterized in that it contains one or more diquaternary polysiloxanes of the formula I,

2Θ

R 'R' R '

I

Z - M - Si-O + Si-0 -Si-M - Z 2 X θ

(I) I

R "R" R "n-1

in the Z a quaternized nitrogen center,

R 'and R "independently of one another are a C] ^ -alkyl radical or an aryl radical, M is a divalent hydrocarbon radical with at least 4 carbon atoms, which preferably has at least one hydroxyl group and is substituted by one or more oxygen atoms and / or groups of the type - C (O) - , -C (O) O- or -C (O) N- may be interrupted, n is a number from 1 to 201 and

X ^{~ represents} an inorganic or organic anion, preference being given to rinse aids which contain one or more diquaternary poly (dimethylsiloxanes) of the formula II,

Z-M- 2 X Θ (II)

R ¹ , R ² , R ³ . R ⁴ , R ⁵ , R ⁷ , R ⁹ , R ¹⁰ independently of one another are C _-22 alkyl or C _2-2 2- alkylene radicals without or with one or more hydroxyl groups or Radicals -CH ₂ -aryl, preferably at least one of the radicals R,

1 1 1

R, R ^"has at least 10 carbon atoms or one of the radicals R,

R ² , R ^{3 is} a benzyl radical,

R ^{C1 represents} an oxygen atom or a Gmppe -N (R), where R represents a Cμ-

Alkyl or hydroxyalkyl radical or hydrogen,

M is a divalent hydrocarbon radical with at least 4 carbon atoms, which preferably has at least one hydroxyl group and is interrupted by one or more oxygen atoms and / or groups of the type - C (O) -, -C (O) O- or -C (O) N- n can be a number from 1 to 201 and X ^"represents an inorganic or organic anion, and those agents are particularly preferred which contain one or more diquaternary poly (dimethylsiloxanes) of the formula III,

in which R is a C ₆ - ₂₂ - alkyl or alkylene radical, in particular a stearyl radical, M represents a spacer of the formula CH ₂ CH (OH) CH ₂ O (CH _{2) 3,} n is a number from 1 to 100, particularly 10, 30 or 50, and X ^{~ represents} an inorganic or organic anion, preferably an acetate ion.

8. rinse aid according to one of claims 6 or 7, characterized in that it is the diquaternary (s) polysiloxane (s) in amounts of 0.001 to 20 wt .-%, preferably from 0.01 to 10 wt .-% , particularly preferably from 0.1 to 5% by weight and in particular from 0.15 to 2.5% by weight, based in each case on the rinse aid.

9. Rinse aid according to one of claims 6 to 8, characterized in that it is surfactant (s), preferably nonionic (s) surfactant (s) and in particular nonionic (s) ten- sid (e) from the group of alkoxylated alcohols, in amounts from 0.1 to 40% by weight, preferably from 0.5 to 30% by weight, particularly preferably from 1 to 20% by weight, and in particular from 2 to 15 wt .-% each based on the rinse aid contains.

10. rinse aid according to one of claims 6 to 9, characterized in that it is non-aqueous solvent (s), preferably ethanol, n-propanol, i-propanol, 1-butanol, 2-butanol, glycol, propanediol, butanediol, glycerol, diglycol , Propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene or ethyl ether, dipropylene glycol - Or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

11. Rinse aid according to one of claims 6 to 10, characterized in that it contains solubilizers, preferably aromatic sulfonates of the formula

includes, in each of the radicals Ri, R _2, R _3, R _4, R ₅ is independently selected from H or a Cι _-5 - alkyl or alkenyl and X is a cation.

12. Rinse aid according to one of claims 6 to 11, characterized in that it contains acidifying agents, preferably organic acids with particular preference for adipic acid, amidosulfonic acid, succinic acid, citric acid, fumaric acid, maleic acid. contains acid, malonic acid, oxalic acid and tartaric acid and mixtures of these acids.

13. Rinse aid according to one of claims 6 to 12, characterized in that it additionally contains one or more substances from the groups of soil-release polymers, dyes and fragrances.

14. Particulate rinse aid for automatic dishwashing, characterized in that it contains 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 fatty substances), d) 0 to 50% by weight of further active substances and / or auxiliaries, and e) 0.1 to 70% by weight of diquaternary polysiloxanes.

15. Particulate rinse aid according to spoke 14, characterized in that it di-quaternary polysiloxanes, preferably diquaternary polysiloxanes of the formula I, particularly preferably diquaternary poly (dimethylsiloxanes) of the formula II and in particular diquaternary poly (dimethylsiloxanes) of the formula III in amounts of 0, 5 to 60 wt .-%, preferably from 1 to 50 wt .-%, particularly preferably from 2.5 to 40 wt .-% and in particular from 5 to 30 wt .-%, each based on the particulate rinse aid.

16. Particulate rinse aid according to one of claims 14 or 15, characterized in that it contains as ingredient b) one or more substances with a melting range between 50 and 100 ° C, preferably between 52.5 and 80 ° C and in particular between 55 and 75 ° C, wherein paraffin waxes with a melting range of 50 ° C to 65 ° C and / or substances from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are preferred coating substances.

17. Particulate rinse aid according to one of claims 14 to 16, characterized in that it additionally contains surfactant (s), preferably nonionic (s) surfactant (s), particularly 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, in each case based on the particulate rinse aid, contains.

18. Detergent molded article for machine dishwashing, containing builders and optionally further ingredients of cleaning agents, characterized in that it contains diquaternary polysiloxanes, preferably diquaternary polysiloxanes of the formula I, particularly preferably diquaternary poly (dimethylsiloxanes) of the formula II and in particular diquaternary poly (dimethylsiloxanes) Formula III in amounts of 0.5 to 60% by weight, preferably 1 to 50% by weight, particularly preferably 2.5 to 40% by weight and in particular 5 to 30% by weight, in each case based on the body weight, contains.

19. Detergent form according to spoke 18, characterized in that the diquaternary polysiloxanes contain in a delayed release form.

20. Multi-phase detergent molded article for machine dishwashing, containing builders and optionally further detergent ingredients, characterized in that at least one phase of a) 0 to 65% by weight> one or more carrier materials, b) 30 to 70% by weight Envelope (s) with a melting point above 50 ° C, c) 0 to 65% by weight of fatty substances), d) 0 to 50% by weight of other active substances and / or auxiliaries, and e) 0.1 to 70% by weight .-% diquaternary polysiloxanes.

21. Mehφhasiger Reinigungsmittelformköφer according spoke 20, characterized in that the phases have the shape of layers and the molded body is 2-, 3- or 4-phase.

22. Mehφhasiger Reinigungsmittelformköφer according spoke 20, characterized in that it consists of a Basisformköφer, which has a cavity, and an at least partially contained in the cavity.

23. Multi-phase detergent molded article according to spoke 22, characterized in that the part contained in the cavity from a) 0 to 10 wt .-%, preferably 0 to 7.5 and in particular 0 to 5 wt .-% 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 fatty substances), d) 0 to 50% by weight, preferably 5 to 45% by weight and in particular 10 to 40% by weight of further active ingredients / or auxiliaries and e) 0.1 to 70 wt .-%>, preferably 1 to 50 wt .-% and in particular 5 to 40 wt .-% diquaternary polysiloxanes.