DE19944416A1 - Rinse aid - 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

The present invention relates to the use of diquaternary polysiloxanes in Detergent and rinse aid for automatic dishwashing. Rinse aid for automatic dishwashing as well as forms of offer, detergents and clear provide dishwashers in a product and the manufacturing processes for such rinse aid and cleaning agents are further objects of the present invention.

Today, machine-washed dishes are often subject to higher requirements than on manually washed dishes. This is how a Ge is completely cleaned of food residues dishes are not rated as perfect if they are washed by machine still whitish spots due to water hardness or other mineral salts which, due to the lack of wetting agents, comes from dried water drops.

In order to obtain glossy and spotless crockery, it is therefore used successfully today Rinse aid. The addition of rinse aid at the end of the wash program ensures that the water runs as completely as possible from the dishes, so that the different waiters surfaces are residue-free and flawlessly shiny at the end of the wash program.

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

Liquid rinse aids are known from EP-B1 0 197 434 (Henkel), which are called nonionic Containing surfactants mixed ethers. In the dishwasher is a variety of different materials (glass, metal, silver, plastic, porcelain) cleaned. This Ma Variety of materials must be wetted as well as possible in the rinse cycle. Rinse aid formulation conditions that only contain mixed ethers as the surfactant component meet these requirements demands not or only to a small extent, so that the rinse aid or drying is unsatisfactory, especially with plastic surfaces.

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

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

The older German patent application DE 198 51 426.3 (Henkel KGaA) describes a Ver drive to the production of multi-phase detergent tablets, in which a Particulate premix is pressed to form bodies which have a trough sen, which later with a separately prepared melt suspension or emulsion from a Envelope and one or more active dispersed or suspended in it substance (s) is filled.

A form of offer that rinse aid to be dosed both separately and by the consumer solid form as well as an additive component to powdered machine dishes detergents can be used, is in the older German patent application DE 199 14 364.1 (Henkel KGaA).

The object of the present invention was to prepare new rinse aids make the at least the same Re regarding the application properties results deliver like marketable rinse aids and beyond that further benefits provide parts. The new rinse aid should be used as a conventional rinse aid tel as well as in the form of combination products and regardless of the Form unfold their advantageous properties. Last but not least, the one Set of new rinse aids also in conventional detergents for the machine Fast dishwashing may be possible. d. H. the funds should also be used as an additional component Lei Enable performance advantages.

It has now been found that the use of diquaternary polysiloxanes in cleaning means beneficial effects for automatic dishwashing. Particularly advantageous It is important if the diquaternary polysiloxanes are used in the rinse cycle reach.

The present invention is therefore in a first embodiment Use of diquaternary polysiloxanes in automatic dishwashing detergents.  

The mere addition of these compounds to cleaning agents has the effect that those with such Clean dishes that have been treated with agents in subsequent cleaning processes rer than dishes that have been washed using conventional means. Here is the Effect regardless of whether the automatic dishwashing liquid, powdery or in tablet form.

As an additional positive effect, the drying time is reduced with that Detergent treated dishes on,. H. after the Ab Take the dishes out of the machine earlier and again during the cleaning program to use.

The invention is characterized by an improved "cleanability" of the treated sub strate in later cleaning processes and by significantly shortening the Drying time compared to comparable agents without the use of diquaternary polysi loxans out. In addition to this primary effect according to the invention, the diquaternary butt unfolds As expected, lysiloxane has the foam-suppressing effect inherent in silicones. Overra shearingly, liquid agents containing diquaternary polysiloxanes point above in addition, not only unaffected by the diquaternary polysiloxane, but also usually even increased cleaning ability and consistently increased cold stability.

The drying time in the context of the teaching according to the invention is generally understood meaning in the sense of the word, i.e. the time that elapses until one in a ge dishwasher-treated dish surface has dried, but especially the Time that passes until 90% of one with a detergent or rinse aid in conc treated or diluted form treated surface is dried.

Diquaternary polysiloxanes in the sense of the invention are polyorganosiloxanes (= silicones) with two quaternized organic ammonium groups, i.e. H. two quaternary nitrogen Atoms, each carrying four organic residues and one of these four residues are bound to a silicon atom of the polyorganosiloxane. According to the invention diquaternary polysiloxanes individually or as mixtures of different diquaternary poly siloxanes used or used in the agent or process.  

It when the diquaternary polysiloxanes in the last rinse cycle, d. H. are present in the rinse aid. This way, the beneficial effect is not weakened by subsequent rinse cycles. Another object of the invention provides hence the use of diquaternary polysiloxanes in the rinse aid of the machine light dishwashing.

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

in the Z a quaternized nitrogen center,
R 'and R "independently of one another are a C _1-4 -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) O- or -C (O) N- can be interrupted
n is a number from 1 to 201 and
X ^{- represents} an inorganic or organic anion,
as described for example in DE 37 19 086 C1 and EP 0 294 642 B1.

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

in the Z the rest

or

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 being} a benzyl radical,
R ^{6 is} an oxygen atom or a group -N (R ⁸ ), where R ^{8 is} a C _1-4 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 is 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 to
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.

Examples of anions suitable according to the invention are, in addition to acetations, 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 available as Tegopren® 6920, Tegopren® 6922 and Tegopren® 6924 from Th. Goldschmidt AG available.

Further examples of diquaternary polysiloxanes of the formula I which are suitable according to the invention to III can be found in DE 37 19 086 C1 and EP 0 294 642 B1.

The use according to the invention can be realized in a simple manner in that the substances mentioned in liquid, powder or tablet detergents or incorporated in rinse aid. Machine dishwashing detergents, the di containing quaternized polysiloxanes are also the subject of the present invention dung.

In preferred embodiments of the present invention, the more detailed nated polysiloxanes in the rinse cycle of automatic dishwashing. Preferred further embodiments of the present invention therefore relate to Klar detergents for automatic dishwashing and combination forms Combine detergent and rinse aid, the latter especially in Powder or tablet form are offered.

Another preferred object of the present invention are rinse aid for machine dishwashing containing diquaternary polysiloxanes.

Such rinse aids are - as described above - by the consumer in the Given the storage tank of the dishwasher, from where it automatically goes into the rinse aid be dosed. Depending on the dosing volume and the capacity of the tank, one is sufficient Tank filling usually 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,

in the Z a quaternized nitrogen center,
R 'and R "independently of one another are a C _1-4 -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 replaced 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,
contain, rinse aids are preferred which contain one or more diquaternary poly (dimethylsiloxanes) of the formula II,

in the Z the rest

or

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 being} a benzyl radical,
R ^{6 is} an oxygen atom or a group -N (R ⁸ ), where R ^{8 is} a C _1-4 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 one or more oxygen atoms and / or groups of the type -C (O) -, -C (O) O- or -C (O) N- un can be broken
n is a number from 1 to 201 and
X ^{- represents} an inorganic or organic anion,
contain 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 ^- an inorganic or organic anion, preferably an acetate, re presented,
contain.

The content of one or more diquaternary polysiloxanes in the inventive Means can vary depending on the application and desired product performance, where in preferred rinse aid according to the invention, the diquaternary polysilox (s) an (e) in amounts of 0.001 to 20 wt .-%, preferably from 0.01 to 10 wt .-%, esp ders preferably from 0.1 to 5 wt .-% and in particular from 0.15 to 2.5 wt .-%, each based on the rinse aid.

The agents according to the invention can furthermore, as surfactant component, anionic, contain nonionic, cationic and / or amphoteric surfactants, nonionic Surfactants are preferred because of their foaming power.

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

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce The mono-, di- and triesters as well as their mixtures are to be understood as Rinestern, as in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Before pulled sulfated fatty acid glycerol esters are the sulfonation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Ca. pric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

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

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 -Fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol esters 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. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

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

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

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

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

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

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

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

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

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

Rinse aids according to the invention which contain a nonionic ten are particularly preferred contain sid, which has a melting point above room temperature. As a result 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, contain.  

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

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

In a preferred embodiment of the present invention, this is nonionic Surfactants with a melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 C- 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 gone.

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

Accordingly, particularly preferred rinse aids according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _6-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, in particular more preferably up to 20% by weight and in particular up to 15% by weight of the total moles mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene Have polyoxypropylene block copolymer units. The alcohol or alkylphenol part such nonionic surfactant molecules preferably make up more than 30% by weight, especially be preferably more than 50% by weight and in particular more than 70% by weight of the total molma such nonionic surfactants. Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxides are units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to Make up 15 wt .-% of the total molecular weight of the nonionic surfactant.

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

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

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 CH ₂ O] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1.5 and y is at least 15.

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

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

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

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

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

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

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

If the latter statements are summarized, rinse aids according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

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

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

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

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

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

Non-aqueous solvents which are used in the agents according to the invention can, for example, come from the group of mono- or polyhydric alcohols, Alka nolamine or glycol ether, provided they are in the specified concentration range with water are miscible. The solvents are preferably selected from ethanol, n- or i- Propanol, butanols, glycol, propane or butanediol, glycerin, diglycol, propyl or Butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethyl lenglycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropy lenglycolmethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1- Butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether so like mixtures of these solvents, so that preferred rinse aid is thereby known are characterized in that they are non-aqueous solvent (s), preferably ethanol, n-propanol, i- Propanol, 1-butanol, 2-butanol, glycol, propanediol, butanediol, glycerin, diglycol, pro pyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol ethyl, ethyl or propyl ether, Dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1- Butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether so such as 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 in the presence of the Hydrotrops, which itself is not a solvent, becomes water-soluble. Substances that a cause such solubility improvement are called hydrotropes or hydrotropes designated. Typical hydrotropes, e.g. B. in the assembly of liquid washing or cleaning agents are xylene and cumene sulfonate. Other substances, e.g. B. urine substance or N-methylacetamide, increase the solubility through a structure-breaking ef fect, 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 solvents, preferably aromatic sulfonates of the formula

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

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

Aromatic sulfonates are particularly preferred in the context of the present invention Toluene, cumene or xylene sulfonate.

Of the two commercially available toluenesulfonates (ortho- and para-toluenesulfonate), the para-isomer is preferred in the context of the present invention. The para-isopropylbenzenesulfonate is also the preferred compound for the cumene sulfonates. Since xylene is usually used industrially as a mixture of isomers, the technically obtainable xylene sulfonate is also a mixture of several compounds which are derived from the sulfonation of ortho-, meta- and para-xylene. In these mixtures of isomers, the compounds dominate in which the following radicals in the general formula I are methyl groups (all other radicals are H): R ₁ and R ₂ , R ₁ and R ₄ , R ₁ and R ₃ and R ₁ and R ₅ . In the case of the xylene sulfonates, there is therefore preferably at least one methyl group ortho to the sulfonate group.

X in the general formula given above represents a cation, for example an alkali metal cation such as sodium or potassium. X can also stand for the charge-equivalent portion 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 present in amounts of 0.2 to 10% by weight preferably from 0.3 to 5% by weight and in particular from 0.5 to 3% by weight, in each case based on the rinse aid.

Acidifying agents can also be added to the rinse aid according to the invention to reduce the pH of the liquor in the rinse aid. Here are so probably inorganic acids as well as organic acids, provided that these with the others Ingredients are compatible. For reasons of consumer protection and handha The solid mono-, oligo- and polycarboxylic acids are particularly safe to use bar. Citric acid, tartaric acid and succinic acid are preferred from this group right, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and also as an acidifying agent in the context of the present invention Sokalan® DCS (trademark of BASF), a mixture from Bern, can preferably be used succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight). Rinse aid which contains acidifying agents, preferably organic acids particular preference for adipic acid, amidosulfonic acid, succinic acid, lemons 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 aid according to the invention can preferably additionally have one or more re substances from the groups of soil release polymers, dyes and fragrances contain. These are described in detail below.  

The rinse aids described above are suitable for dosing from the stock stank of standard dishwashers. The preferred use according to the invention diquaternary polysiloxanes can also be achieved by dissolving Offered forms are provided by the consumer before the start of the Reini dosing in the dishwasher, but the active ingredients only in the Release rinse aid. This has the advantage that the consumer only has one product - instead of two - must dose.

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

• a) 0 to 65% by weight of one or more carrier materials,
• b) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,
• c) 0 to 65% by weight of fat (s),
• d) 0 to 50% by weight of further active substances and / or auxiliaries and
• e) 0.1 to 70 wt .-% diquaternary polysiloxanes

contains.

All substances which are solid at room temperature are suitable as carrier substances a). Usually you will select fabrics that add an additional one in the cleaning cycle Developing an effect, with builders being particularly suitable. In preferred vehicles Partial particulate rinse aids are substances from the Group of water-soluble detergent and cleaning agent ingredients, preferably the Carbonates, hydrogen carbonates, sulfates, phosphates and those solid at room temperature organic oligocarboxylic acids in amounts of 35 to 60% by weight, preferably 40 up to 55 wt .-% and in particular from 45 to 50 wt .-%, each based on the part weight, included.

The preferred carriers mentioned are described in detail below.

The particulate rinse aid can also be formulated without carrier materials and thus only consist of the ingredients b) to e). The production of such Components are usually made by shaping a melted  NEN mix of ingredients. Rinse aid particles containing carrier material can for example by spraying, spraying or pouring such a melt onto the carrier germ materials are obtained.

The manufacturing processes are described below; a description follows of the ingredients b) to d), the amounts given being clear on the carrier material Obtain detergent particles. If you want to produce carrier-based particles, refer to them The information below relates to the composition of the mixture / melt that is applied to the carrier, the proportion of the particle resulting from the proportions of Mixture and carrier material in the particle results.

To the coating substances which are used in the rinse aid particles according to the invention, there are various requirements, on the one hand the melting or Solidification behavior, but also the material properties of the coating in the solidified state, d. H. in the rinse aid particle. Because the rinse aid particles Transport or storage should be permanently protected against environmental influences Envelope has a high stability compared to, for example, packaging or transport have occurring shock loads. The coating substance should at least either have partially elastic or at least plastic properties to a occurring shock load to react by elastic or plastic deformation and not to break. The coating substance should have a melting range (solidification range) in one have such a temperature range in which none of the active substances to be coated exposed to high thermal loads. On the other hand, the melting range however, be sufficiently high to have another at least slightly elevated temperature to provide effective protection for the enclosed active substances. According to the invention the coating substances have a melting point above 30 ° C.

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

The coating substance preferably has a melting range which is between approximately 45 ° C. and is about 75 ° C. In the present case, this means that the melting range within the specified temperature interval occurs and does not denote 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 usually melt above 40 ° C without decomposition and a little above the Melting point are relatively low viscosity and not stringy. You assign one strongly temperature-dependent consistency and solubility.

According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as Petrolatum, paraffin waxes or micro waxes.

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

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. Connections can also be used as covering materials from other classes of substances that meet the stated softening point requirements fulfill. Suitable synthetic compounds have, for example, higher esters of Phthalic acid, especially dicyclohexyl phthalate, commercially available under the name Unimoll® 66 (Bayer AG) is available. Synthetic ones are also suitable Waxes from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, the  is available under the name Cosmacol® ETLP (Condea). Are reversed too synthetic or semi-synthetic esters from lower alcohols with fatty acids from native Sources can be used. Tegin® 90 (Goldschmidt), for example, falls into this class of substances Glycerol monostearate palmitate. Also shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH) can be used according to the invention as a covering material.

The waxes, for example, are also included in the scope of the present invention so-called wax alcohols. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols usually with about 22 to 40 carbon atoms. The Wax alcohols, for example, come in the form of wax esters of higher molecular weight Fatty acids (wax acids) as the main component of many natural waxes. examples for Wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or Melissyl alcohol. The coating of the solid particles coated according to the invention can optionally also contain wool wax alcohols, including triterpenoid and Steroidal alcohols, for example lanolin, means that, for example, under the Trade name Argowax® (Pamentier & Co) is available. Also at least in part can be used as part of the envelope within the scope of the present invention Fatty acid glycerol esters or fatty acid alkanolamides, but optionally also water-insoluble ones or only slightly water-soluble polyalkylene glycol compounds.

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

Paraffin waxes have a frame compared to the other natural waxes mentioned The present invention has the advantage that in an alkaline Detergent environment no hydrolysis of the waxes takes place (as for example  is to be expected in the wax esters), since paraffin wax has no hydrolyzable groups contains.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of below 60 ° C on parts of high-melting alkanes in the paraffin this melting temperature in the detergent fleet undesirable wax residues on the surfaces to be cleaned or the goods to be cleaned. Such Wax residues usually lead to an unsightly appearance of the cleaned Surface and should therefore be avoided.

Preferred particulate rinse aids contain at least one paraf as the coating substance Finwax with a melting range from 50 ° C to 60 ° C.

The content of the paraffin wax used is preferably at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes if possible high. The more solid wax components in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing share of Solid wax components increase the resilience of the rinse aid particles to impacts or rubbing against other surfaces, resulting in longer lasting protection of the Particle leads to active substances. High levels of oils or liquid wax components can lead to a weakening of the particles, which opens pores and the active substances be exposed to the environmental influences mentioned at the beginning.

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

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

The principle described above serves to delay the release of ingredients a certain time in the cleaning cycle and can be particularly advantageous use if in the main wash cycle at a lower temperature (e.g. 55 ° C) is rinsed so that the active substance from the rinse aid particles only in the rinse aid higher temperatures (approx. 70 ° C) is released.

Preferred particulate rinse aids contain one or more substances as the coating substance with a melting range of 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably as from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the particle weight, preference being given to particle-shaped ones which contain egg b NEN 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, Paraf Finaxes with a melting range from 50 ° C to 65 ° C and / or substances from the group of the polyethylene glycols (PEG) and / or polypropylene glycols (PPG) preferred enveloping are punching.

As a third ingredient, the detergent components according to the invention can be used contain one or more fatty substances, preferred detergent components characterized in that as ingredient c) they are 1 to 60, preferably 5 to 55, particularly preferably contain 10 to 50 and in particular 20 to 45% by weight of fat (s).

Under fatty substances c) in the context of this application at normal temperature (20 ° C) liquid to solid substances from the group of fatty alcohols, fatty acids and fatty acids derivatives, especially the fatty acid esters, understood. Implementation products from Fettalko fetching with alkylene oxides as well as the salts of fatty acids count within the scope of the present registration for surfactants (see above) and are not fatty substances in the sense of the Er finding. According to the invention, preferred fatty substances are fatty alcohols and fatty alcohols  Hol mixtures, fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or use polyols, fatty acid amides, fatty amines etc.

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

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

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

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

The esters of fatty acids with alkanols, diols or polyo can be used as fatty acid esters Use len, with fatty acid polyol esters being preferred. Com. As fatty acid polyol ester Men mono- or diesters of fatty acids with certain polyols into consideration. The fatty acid Ren, which are esterified with the polyols are preferably saturated or unsaturated Fatty acids with 12 to 18 carbon atoms, for example lauric acid, myristic acid, palmitin acid or stearic acid, preferably the technically obtained mixtures of the fatty acid ren are used, for example those derived from coconut, palm kernel or tallow fat acid mixtures. In particular acids or mixtures of acids with 16 to 18 C Atoms such as tallow fatty acid are for esterification with the polyvalent Al suitable for alcohol. As polyols, who are esterified with the above-mentioned fatty acids in the context of the present invention, sorbitol, trimethylolpropane, Neopentyl glycol, ethylene glycol, polyethylene glycols, glycerin and polyglycerols in Be dress.

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

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

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

The other detergent ingredients, which as component d) in the Invention How rinse aid can be incorporated is described in detail below ben.

The particulate rinse aid according to the invention contains diquater as ingredient e) nary polysiloxanes, the above statements regarding preferred species apply completely analogously. To avoid redundancies, therefore, the above mentioned Formulas referenced. Preferred particulate rinse aid contain diquaternary Polysiloxanes, preferably diquaternary polysiloxanes of formula I, particularly preferred 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 of 1 to 50 wt .-%, particularly preferably from 2.5 to 40 wt .-% and in particular from 5 to 30% by weight, based in each case on the particulate rinse aid.

Another object of the present invention is a method for producing particulate detergent components, which is characterized in that a melt from

• a) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,
• b) 0 to 65% by weight of fat (s),
• c) 0 to 50% by weight of further active substances and / or auxiliaries and
• d) 0.1 to 70% by weight of diquaternary polysiloxanes

applied to one or more carrier materials and the mixture is shaped tet.  

In this process variant, a melt is first produced, the further active and may contain auxiliary substances. This is placed on a carrier material and in Mi processing with this carrier material.

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

The melt can be applied to the carrier material in all customary mixtures devices are carried out. The shaping processing step for the Ge Mix of melt and carrier material is also not subject to any process engineering Restrictions, so that the person skilled in the art can also make use of the processes familiar to him can choose. In the applicant's attempts, methods have proven to be preferred where the shaping processing by granulating, compacting, peeling animals, extruding or tableting.

The method according to the invention comprises the application of melts from the contents substances a) to d) on carrier materials. In principle, melt and carrier (s) can be in varying amounts may be contained in the resulting rinse aid particles. Preferred Processes are characterized in that a mixture of 5 to 50 wt .-%, before preferably 10 to 45% by weight, particularly preferably 15 to 40% by weight and in particular 20 up to 35% by weight of a melt from 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 up to 80 wt .-% carrier material (ien) is processed shaping.

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

The detergent components according to the invention can also be free of carrier material be formulated so that they consist only of the ingredients a) to d). To Her  have particulate detergent components according to the invention in particular the prilling, the pastilling and the scaling by means of a cooling roller zen proven.

Another object of the present invention is therefore in a first embodiment, a method for producing prilled detergent components, in which a melt is made

• a) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,
• b) 0 to 65% by weight of fat (s),
• c) 0 to 50% by weight of further active substances and / or auxiliaries and
• d) 0.1 to 70% by weight of diquaternary polysiloxanes

injected into a cold gas stream.

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

In general, all gases can be used as the cold gas stream, the Temperature of the gas is below the melting temperature of the melt. Long time To avoid falling stretches, 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 by the choice of droplet size particle sizes 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 method for producing pastilized detergent components, in which a melt is made

• a) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,
• b) 0 to 65% by weight of fat (s),  
• c) 0 to 50% by weight of further active substances and / or auxiliaries and
• d) 0.1 to 70% by weight of diquaternary polysiloxanes

dosed on chilled pastilles.

Pastilling, sometimes referred to as pelleting, includes the dose tion of the melt from the ingredients a) to d) on rotating, inclined plates, one Have temperature below the melting temperature of the melt and preferably be cooled below room temperature. Process variants can also be used here in which the pastilles are frozen. Here, however Measures against the condensation of air humidity are taken.

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

As an even more cost-effective variant for the production of particulate detergent components of the above-mentioned composition from melts, the use of cooling rollers is appropriate. Another object of the present invention is therefore a process for the production of particulate detergent components, in which a melt is made

• a) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,
• b) 0 to 65% by weight of fat (s),
• c) 0 to 50% by weight of further active substances and / or auxiliaries and
• d) 0.1 to 70% by weight of diquaternary polysiloxanes

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

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

The rinse aid particles according to the invention can be directly available to the consumer be given so that he also doses them to the cleaning agent as required.  

Because of this additional dosing step, however, would be in addition to the fixed form of supply and the addition in the same dosing compartment the advantages over liquid rinse aid minimized. It is therefore preferred to particle the rinse aid particles according to the invention to form machine dishwashing detergents.

Another object of the present invention is therefore also a particulate automatic dishwashing detergent containing builders and optional additional contents substances from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosis onsinhibitoren, polymers, dyes and fragrances that a particle of the invention shaped rinse aid in amounts of 0.5 to 30% by weight, preferably 1 to 25% by weight and in particular from 5 to 15% by weight, based in each case on the total average.

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

The most important ingredients in automatic dishwashing detergents are builders. In the cleaning agents according to the invention for machine dishwashing all builders commonly used in detergents and cleaning agents hold, especially zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological concerns about their use - including the phosphates. The builders mentioned below are all used as carrier materials for the inventors suitable rinse aid particles according to the invention, as already explained above.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. 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 O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in the 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 and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline ranges of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a release delay compared to the conventional water glass glasses, are described for example in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from 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 was developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through the formula

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

can be described. Suitable zeolites have an average particle size of we less than 10 µm (volume distribution; measurement method: Coulter Counter) on and included preferably 18 to 22% by weight, in particular 20 to 22% by weight of bound water.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons should be. Among the large number of commercially available phosphates, the Alka limetal phosphates with particular preference for pentasodium or pentapotassium tri phosphate (sodium or potassium tripolyphosphate) in detergents and cleaning agents Industry the most important.

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 or lime incrustations in tissues and also contribute to cleaning performance.

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

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

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

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

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

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] that crystallizes with 6 H ₂ O. _n -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 20 ° approx. 20 g, at 100 ° around 32 g of the salt free of water; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polypho 70220 00070 552 001000280000000200012000285917010900040 0002019944416 00004 70101sphate are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

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

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphos phate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tri Polyphosphate and sodium potassium tripolyphosphate can be used according to the invention.  

As organic cobuilders in the dishwasher according to the invention agents in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, As Paraginic acid, polyacetals, dextrins, other organic cobuilders (see below) and Phosphonates are used. These classes of substances are described below.

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

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

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass 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 respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, are preferred his.

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

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

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

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

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

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

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 50,000 g / mol. There is a poly saccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30,000 g / mol.

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

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

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

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

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

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

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.

Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying peracidic salts or peracids, such as per benzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) 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 paproacidaproic acid ], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiperoxyacidoxydiperbutylacid, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

As a bleach in the cleaning agents according to the invention for the machine Dishwashing can also use chlorine or bromine-releasing substances. Suitable chlorine or bromine releasing materials include, for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleaches mentioned can also be used to achieve "post-bleaching" in rinse aid all or part of the inventive rinse aid particles in the invention machine dishwashing detergent are introduced.

Bleach activators that support the action of the bleach have already been added mentioned above as a possible ingredient of the rinse aid particles. Known bleach activators  are compounds that contain one or more N- or O-acyl groups, such as Substan zen from the class of anhydrides, esters, imides and acylated imidazoles or Oximes. Examples are tetraacetylethylene diamine TAED, tetraacetyl methylene diamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1.5- Diacetyl-2,2-dioxohexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators cal peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms Atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated tria Zinderivate, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acy gelled Glycolurile, in particular tetraacetylglycoluril (TAGU), N-acylimide, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol koldiacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well as acetylated sorbitol and mannitol as their mixtures (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose and acety gelled, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated Lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and Acyl lactams are also preferred. Combinations of conventional ones Bleach activators can be used.

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

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

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

Enzymes in particular come from the cleaning agents according to the invention from the classes of hydrolases such as proteases, esterases, lipases or lipolytic acting enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases help to remove stains such as protein, greasy or starchy stains. Oxidoreductases can also be used for bleaching be used. Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and en derived from their genetically modified variants active enzymatic agents. Proteases of the subtilisin type and esp special proteases obtained from Bacillus lentus. Here are En  enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes, in particular special however protease and / or lipase-containing mixtures or mixtures with lipo enzymes of particular interest. Examples of such lipolytic acting enzymes are the well-known cutinases. Also have peroxidases or oxidases proved to be suitable in some cases. Suitable amylases include in particular special alpha-amylases, iso-amylases, pullulanases and pectinases.

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

Dyes and fragrances can be used in the dishwasher detergents according to the invention can be added to improve the aesthetic impression of the resulting products and to the consumer, in addition to the performance, a visually and sensory "typical and unmatched interchangeable "product. As perfume oils or fragrances can individual fragrance compounds, e.g. B. the synthetic products of the ester type, Ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Smell Compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p- tert-Butylcyclohexylacetate, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylace tat, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example, benzylethyl lether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, Citral, Citronel lal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeo nal, to the ketones z. B. the Jonone, α-isomethylionone and methylcedryl ketone to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and ter pineol, the hydrocarbons mainly include terpenes such as limonene and Pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such perfume oils can also be natural che fragrance mixtures contain, as they are accessible from plant sources, for. B.  Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning agents according to the invention be, but it can also be advantageous to apply the fragrances to carriers that the Increase the adhesion of the perfume to the laundry and by a slower fragrance release the long-lasting fragrance of the textiles. As such have backing materials Cyclodextrins have proven themselves, for example, the cyclodextrin-perfume complexes can also be coated with other auxiliaries. Also an inconsistency ration of the fragrances in the rinse aid particles according to the invention is possible and leads to a scent impression when opening the machine (see above).

In order to improve the aesthetic impression of the agents produced according to the invention, it (or parts of it) can be colored with suitable dyes. Preferred Dyes, the selection of which is not difficult for a person skilled in the art, have one high storage stability and insensitivity to the other ingredients of the Means and against light as well as no pronounced substantivity towards those with the Substrates to be treated such as glass, ceramics or plastic tableware to these not to stain.

The cleaning agents according to the invention can protect the items to be washed or the Ma schine corrosion inhibitors contain, especially silver protection in the area of automatic dishwashing have a special meaning. The be knew substances of the prior art. In general, silver protection in particular medium selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes be used. Benzotriazole and / or alkyl are particularly preferably to be used aminotriazole. Active chlorine is also often found in cleaner formulations agents that can significantly reduce the corrosion of the silver surface. In chlorine Free cleaners are especially oxygen and nitrogen-containing organic redox acti  ve compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of this compound classes. Also salt-like and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Are preferred here the transition metal salts selected from the group consisting of manganese and / or Cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or Manganese and manganese sulfate. Zinc compounds can also be used for prevention corrosion on the wash ware.

The composition of the rinse aid particles according to the invention is so ge ensures that they are not in the main wash cycle (and also in optional pre-wash cycles) or only dissolve to a minor extent. This ensures that the active substances are only released in the rinse aid cycle and develop their effect here. Besides this Depending on the type of dishwasher, chemical assembly is a physical one Packaging required so that the rinse aid particles when changing water in the The machine cannot be pumped out and is therefore no longer available for the rinse aid stand. Domestic dishwashers contain some in front of the drain pump the water or the cleaning solution from the measure after the individual cleaning cycles pump pumps, a sieve insert that prevents the pump from becoming clogged with dirt should hinder. If heavily soiled crockery is washed by the consumer, it must Sieve insert to be cleaned regularly, which is due to the easy accessibility and Removability is easily possible. The rinse aid particles according to the invention are now preferably designed in terms of their size and shape so that they the sieve set the dishwasher even after the cleaning cycle, d. H. after exposure to Movement in the machine and the cleaning solution, do not happen. In this way it is ensured that there are rinse aid particles in the dishwasher in the rinse cycle are located under the influence of the warmer water the Aktivsub Release punch (s) and bring the desired rinse aid effect. As part of the present Preferred inventive particulate machine dishwashing detergents are thereby characterized in that the particulate rinse aid has particle sizes between 1 and 40 mm,  preferably between 1.5 and 30 mm and in particular between 2 and 20 mm having.

In the dishwashing detergents according to the invention, the rinse aid particles can be mixed with the above sizes mentioned from the matrix of the other particulate ingredients protrude, but the other particles can also have sizes that mentioned Range, so that a total of a detergent is formulated, which consists of large Detergent and rinse aid particles. Especially when the fiction moderate rinse aid particles, for example a red, blue, green or have yellow color, it is for the appearance of the product, i. H. of the total detergent is an advantage if the rinse aid particles are visibly larger than that Matrix of the particles of the other ingredients of the cleaning agent. Here are invented Particulate machine dishwashing detergent according to the invention preferred, which (without Be taking into account the rinse aid particles) particle sizes between 100 and 3000 µm preferably between 300 and 2500 microns and in particular between 400 and 2000 microns point.

The visual appeal of such compositions can be in addition to the color of the rinse aid particles also by contrasting coloring of the powder matrix or by the shape of the Rinse aid particles are increased. Since the manufacture of rinse aid particles relies on tech nically uncomplicated procedures can be used, it is easily possible to offer them in various forms. In addition to the particle shape, which approx hernd spherical shape are, for example, cylindrical or cube-shaped particles can be manufactured and used. Other geometric shapes can also be realized. Spec All product designs can, for example, have star-shaped rinse aid particles contain. Also disks or shapes that form the base of plants and carcasses for example show tree, flower, blossom, sheep, fish etc., can be easily produced. Interesting visual incentives can also be created in this way by: which produces rinse aid particles in the form of a stylized glass to achieve the rinse aid effect also to emphasize optically in the product. There are no limits to your imagination puts.  

If the cleaning agents according to the invention are formulated as a powder mixture, it can - especially in the case of very different sizes of rinse aid particles and detergent agent matrix - on the one hand partial separation when the package is shaken occur, on the other hand, the dosage in two successive cleaning courses be different, since the consumer does not always necessarily have the same amount of cleaning detergent and rinse aid particles. Should be desired, technically one always To use the same amount per cleaning cycle, this can be done by the person skilled in the art The packaging of the agents according to the invention in bags made of water-soluble film is reali be settled. Also particulate machine dishwashing detergents in which a Do Siereinheit is sealed in a bag made of water-soluble film, are counter stood of the present invention.

As a result, the consumer has only one bag, for example a cleaning contains medium powder and several optically prominent rinse aid particles in the dosage to put in his dishwasher. This embodiment of the present Invention is therefore a visually appealing alternative to conventional cleaning agents tablet tablets.

The cleaning agents according to the invention can be produced in a manner known per se len. A process for the production of powdered dishwasher detergents Rinse aid effect, in which a powdered machine dishwasher known per se is mixed with rinse aid particles according to the invention, is therefore another Subject of the present invention.

The desired retention of the rinse aid particles in the Ma The machine can also be used for water changes in addition to the enlargement mentioned above Realize rinse aid particles by reducing the holes in the sieve insert. In this way you can formulate automatic dishwashing detergents that are uniform have average particle size which is smaller than, for example, 4 to 12 mm. For this purpose, the product according to the invention, in which the rinse aid particles are also clogged have larger particle sizes, a sieve insert is added, which be in the machine sensitive insert replaced or covers. Another subject of the present inven  Therefore, manure is a kit-of-parts that contains a powdered machine according to the invention Dishwashing detergent and a sieve insert for household dishwashers.

As already mentioned, the combination of agent and sieve according to the invention allows set the formulation of funds in which the rinse aid particles are less have sizes. Kits-of-parts according to the invention, in which the particle sizes of the automatic dishwashing detergent (taking into account the rinse aid particles) in the Be range from 400 to 2500 µm, preferably from 500 to 1600 µm and in particular from 600 up to 1200 µm are preferred.

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

The kit of parts according to the invention is not based on the specific shape of the sieve insert limited, in which this replaces or covers the insert in the machine. According to the invention, it is also possible and preferred for the kit of parts to have a sieve insert enclose, which has the shape of a basket that in a known manner in the Ge dishwasher - for example on the cutlery basket - can be hung. On in this way a sieve insert designed in this way replaces the dosing chamber, d. H. the consumer doses the dishwasher detergent according to the invention directly into this sieve insert in the cleaning and rinse cycle described above Wise works.

The advantages according to the invention can also be offered in the compact form Shaped body can be used. Another object of the present invention is there forth also containing a detergent tablet for automatic dishwashing Builders and optionally other ingredients of cleaning agents, the diquaternary Polysiloxanes, preferably diquaternary polysiloxanes of formula I, particularly preferred 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 of 1 to 50 wt .-%, particularly preferably from 2.5 to 40 wt .-% and in particular from 5 to 30 wt .-%, each based on the weight of the molded body contains.

Here too, reference can be made to the above information with regard to preferred embodiments to get expelled. As already mentioned, the introduction of the diquaternary polysiloxanes particularly preferred in the rinse cycle, so that preferred detergent tablets are characterized in that they dissolve the diquaternary polysiloxanes Form included.

Not only is a release delay particularly preferred, but a controlled one Release that is not due to slower solubility but due to external circumstances controlled release. The rinse aid particles described above can can also be formulated as a molded body phase and also offer the possibility in molded bodies possibility of temperature-controlled release of the diquaternary polysiloxanes.

Another object of the present invention are therefore multi-phase detergent tablets for machine dishwashing, containing builders and optional other detergent ingredients in which at least one phase consists

• a) 0 to 65% by weight of one or more carrier materials,
• b) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,
• c) 0 to 65% by weight of fat (s),
• d) 0 to 50% by weight of further active substances and / or auxiliaries and
• e) 0.1 to 70 wt .-% diquaternary polysiloxanes

consists.

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

The individual phases of the shaped body can be within the scope of the present invention have different spatial shapes. The simplest possible implementation is  in two or multi-layer tablets, each layer of the shaped body one Represents phase. However, it is also possible according to the invention to produce multiphase moldings Deliver in which individual phases take the form of inclusions in another phase (s) exhibit. In addition to so-called "ring-core tablets" there are, for example, casings abletten or combinations of the embodiments mentioned possible. examples for multi-phase moldings can be found in the illustrations of EP-A-0 055 100 (Jeyes), the Toilet cleaning blocks describes. The most technically widespread spatial form at the moment phase shaped body is the two- or multi-layer tablet. As part of the present According to the invention, it is therefore preferred that the phases of the shaped body take the form of layers have and the molded body is 2-, 3- or 4-phase.

The moldings according to the invention can take on any geometric shape where with in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthor hombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, seven- and octagonal- prismatic and rhombohedral shapes are preferred. Completely irregular too Base areas such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped bodies according to the invention have corners and edges, these are preferred wisely rounded. As an additional optical differentiation, an embodiment with rounded corners and chamfered ("chamfered") edges preferred.

Instead of the layer structure, it is also possible to produce moldings which are the part of the invention moderate detergent component in the form of other phases. Here it is proven to produce base moldings which have one or more cavity (s) and the melt from the ingredients a) to d) of the cleaning agent according to the invention Fill the tel component into the cavity and allow it to solidify there. By this man Positioning process, preferred multiphase detergent tablets result from a base molding which has a cavity and an at least partially part contained in the cavity.

The cavity in the pressed part of such shaped bodies according to the invention can in any case have de shape. You can cut through the molded body, d. H. an opening at various  which have sides, for example on the top and bottom of the molded body, it can but also a cavity that does not go through the entire molded body, the opening thereof is only visible on one side of the molding. The shape of the cavity can also vary widely zen can be chosen freely. For reasons of procedural economy, there have been continuous Holes, the openings of which lie on opposite surfaces of the shaped bodies, and wells with an opening on one side of the molded body have proven successful. In preferred washing and detergent tablets, the cavity has the shape of a through hole on, the openings of which are located on two opposite shaped body surfaces. The The shape of such a through hole can be chosen freely, with molded body are preferred in which the through hole is circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal Hori has zonal sections. Also completely irregular hole shapes like arrow or animal shapes, Trees, clouds, etc. can be realized. As with the moldings are in In the case of angular holes, those with rounded corners and edges or with rounded preferred corners and chamfered edges.

The geometric implementation forms mentioned above can be combined as desired combine other. Shaped bodies with a rectangular or square base can round holes as well as round shaped bodies with achtec holes, with no limit to the variety of possible combinations are. For reasons of process economy and aesthetic consumer perception Shaped articles with a hole are particularly preferred in which the shaped body base area and the hole cross section have the same geometric shape, for example shaped bodies with square base and centrally integrated square hole. Especially ring shaped bodies are preferred, i. H. circular shaped body with a circular hole.

If the above Principle of the hole open on two opposite sides of the molded body is reduced to an opening, mold bodies are obtained. According to the invention Detergent tablets in which the cavity is in the form of a trough has are also preferred. As with the "perforated bodies", they can be invented molded article according to the invention also in this embodiment, any geometric shape assume, in particular concave, convex, biconcave, biconvex, cubic, tetra  gonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped ge, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, you rectangular and octagonal prismatic and rhombohedral shapes are preferred. Also completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. will be realized. If the molded body has corners and edges, these are preferred rounded. As an additional optical differentiation is an embodiment with abge rounded corners and chamfered ("chamfered") edges preferred.

The shape of the trough can also be chosen freely, with molded bodies being preferred which at least one trough has a concave, convex, cubic, tetragonal, orthorhombi cal, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dode cathedral, octahedral, conical, pyramidal, ellipsoid, five, seven and octagonal prismatic and rhombohedral shape can take. Completely irregular Mul too shapes such as arrow or animal shapes, trees, clouds, etc. can be realized. As with the molded bodies, troughs are with rounded corners and edges or with rounded corners and chamfered edges preferred.

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

• a) 0 to 10 wt .-%, preferably 0 to 7.5 and in particular 0 to 5 wt .-% of one or several carrier materials,
• b) 30 to 70% by weight, preferably 35 to 65% by weight and in particular 40 to 60% by weight Envelope (s) with a melting point above 50 ° C,
• c) 0 to 65% by weight, preferably 10 to 60% by weight and in particular 20 to 50% by weight Fat (s),
• d) 0 to 50% by weight, preferably 5 to 45% by weight and in particular 10 to 40% by weight further active substances and / or auxiliary substances as well
• e) 0.1 to 70% by weight, preferably 1 to 50% by weight and in particular 5 to 40% by weight diquaternary polysiloxanes

consists.

The size of the trough or through hole compared to the overall shape body depends on the intended use of the molded body. Depending on with how much more active substance the remaining hollow volume is filled should and whether contain a smaller or larger amount of detergent component the size of the cavity may vary. Regardless of the intended use Detergent tablets are preferred in which the volume ratio of pressed part ("base molding") to detergent component 2: 1 to 100: 1, before preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1, is.

In addition to the volume ratio mentioned, a mass ratio of the two can also be used Parts are given, the two values on the densities of the base molding or correlate the detergent component with each other. Independent of Density of the individual parts are detergent tablets according to the invention per preferred, in which the weight ratio of the base molding to cleaning agent tel component 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1.

Analogous information can also be given for the surfaces, each from the base molded body or from the detergent component are visible. Here are laundry or detergent tablets are preferred, in which the externally visible surface surface of the detergent component 1 to 25%, preferably 2 to 20%, particularly be preferably 3 to 15% and in particular 4 to 10% of the total surface of the shaped body matters.

The detergent component and the base molding are preferably optically un colored differently. In addition to the optical differentiation, application technology cal advantages through different solubilities of the different shaped body areas be achieved. Detergent tablets, in which the cleaning middle component dissolves faster than the base molding, are preferred according to the invention.  

By incorporating certain components, the solubility of the Reini Component can be accelerated in a targeted manner, on the other hand, the release certain ingredients from the detergent component for advantages in washing or cleaning process.

Of course, detergent tablets according to the invention are also molded preferred, in which the detergent component dissolves later in the washing program than the base molding. Performance benefits from this delayed release can be seen achieve, for example, that with the help of a more slowly soluble cleaning agent tel component active substance (s) are only released in later rinses. So can for example in automatic dishwashing due to slow-dissolving cleaning medium components are achieved that in the rinse aid further active substance (s) Is available. Through additional substances such as non-ionic surfactants, acidification detergents, soil release polymers etc. can be used to improve rinse aid results. Incorporation of perfume is also possible without any problems; by its delayed In dishwashers, release can cause the "lye smell" that often occurs in Opening the machine can be eliminated. The ingredients acidifying agent, should- Release polymers etc. are on the detergent components of the invention then related ingredients d).

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

In order to facilitate the disintegration of highly compressed moldings, it is possible to disintegrate on aids, so-called tablet disintegrants, to incorporate them into the disintegration to shorten times. Under tablet disintegrants or disintegrators according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical Technologie "(6th edition, 1987, pp. 182-184) understood auxiliary substances that are necessary for the rapid  Disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in provide resorbable form.

These substances, which are also referred to as "explosives" due to their effect, ver increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known disintegration aid medium are, for example, carbonate / citric acid systems, but also other organic ones Acids can be used. Swelling disintegration aids are, for example synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or mo differentiated natural substances such as cellulose and starch and their derivatives, alginates or casein Derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids tel, each based on the weight of the molded body. Contains only the basic molding Desinte tion aids, the information given relates only to the weight of the ba molded body. In the incorporation of disintegration aids in the Invention modern detergent components 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 form such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6 % By weight. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally considered, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the disintegrating agent based on cellulose. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not finely divided form, but before mixing into the premixes to be pressed converted into a coarser form, for example granulated or compacted. Washing and Detergent tablets, the disintegrant in granular or optionally cogranu Contained form, are in the German patent applications DE 197 09 991 (Ste fan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO 98/40463 (Henkel). These writings are also more detailed information on the Her position of granulated, compacted or cogranulated cellulose disintegrants men. 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 to at least 90% by weight between 400 and 1200 µm. The above and in the writings cited described coarser disintegration aids on cellulose In the context of the present invention, bases are preferred as disintegration aids used and commercially, for example under the name Arbocel® TF-30-HG by available from Rettenmaier.

As a further disintegrant based on cellulose or as part of this compo microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged. A  subsequent disaggregation of the microfine cellulo produced by the hydrolysis sen supplies the microcrystalline celluloses, which have primary particle sizes of approx. 5 µm sen and, for example, to granules with an average particle size of 200 microns are pactable.

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

The detergent tablets according to the invention can moreover both in Basic molded body as well as a gas-developing brew in the detergent component system included. The gas-developing shower system can consist of a single substance exist, which releases a gas on contact with water. Among these connections is ins special to call the magnesium peroxide, which releases oxygen on contact with water puts. Usually, however, the gas-releasing bubble system itself consists of min at least two components that react with one another to form gas. While here one Many systems are conceivable and executable, for example nitrogen, oxygen or release hydrogen, it will in the washing and cleaning according to the invention Fibrous system used bubble system based on both economic and let choose based on ecological considerations. Preferred shower systems best hen from alkali metal carbonate and / or hydrogen carbonate and an acidification medium, which is suitable to free carbon dioxide from the alkali metal salts in aqueous solution clog.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium are salts are clearly preferred over the other salts for cost reasons. Self ver the pure alkali metal carbonates or -hydrogen carbonates are used; rather, mixtures of different car bonates and hydrogen carbonates may be preferred for washing technology reasons.  

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 car bonates or bicarbonates and 1 to 15, preferably 2 to 12 and in particular 3 up to 10% by weight of an acidifying agent, in each case based on the total shaped body per, used.

As an acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihy drug phosphates and other inorganic salts can be used. However, are preferred organic acidifiers are used, with citric acid being particularly preferred added acidifier. However, the other fixed ones can also be used in particular Mono-, oligo- and polycarboxylic acids. Wine is preferred from this group acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid like polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid are also a settable. Commercially available and as an acidifying agent in the context of the present Sokalan® DCS (trademark of BASF) is also preferably used according to the invention Mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adi pinic acid (max. 33% by weight).

In the context of the present invention, preference is given to detergent tablets a substance from the group of organic as an acidifying agent in the shower system Di-, tri- and oligocarboxylic acids or mixtures of these can be used.

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

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

calculate, where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h.

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

The relative equilibrium humidity of 85% at 23 ° C can be found, for example, in La Borehouses with moisture control to +/- 2% r. Adjust L. exactly. Even over saturated solutions of certain salts form in closed systems constant and well-defined relative humidity at a given temperature, that on the phase equilibrium between partial pressure of water, saturated solution and soil body are based.

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

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

The packaging system of the combination according to the invention encloses depending on the design Form of the invention a certain amount of cleaning agent according to the invention component, a certain amount of a particulate detergent setting or one or more detergent tablets. It is there preferred according to the invention, either to design a shaped body such that it has a Application unit of the detergent and cleaning agent includes, and this molded body  to be packed individually, or to pack the number of moldings in one packaging unit ken, which comprises an application unit in total. At a target dosage of 80 g According to the invention, detergents and cleaning agents are possible, a 80 g weight To manufacture detergent tablets and to pack them individually, it is According to the invention, however, it is also possible to use two washing and cleaning agents weighing 40 g each Packing the shaped body into a packaging to form a combination according to the invention to get. This principle can of course be expanded, so that fiction three, four, five or even more detergents and cleaning agents according to combinations can contain molded articles in a packaging unit. Of course, two can or more moldings in one package have different compositions sen. In this way it is possible to spatially separate certain components separate, for example to avoid stability problems.

The packaging system of the combination according to the invention can differ from the materials and take on any external shape. From economic For reasons of and for reasons of easier processability, however, there are packaging systems Steme preferred, in which the packaging material is light in weight, easily process and is 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, i. H. as loose bulk tion, be filled into a bag made of the materials mentioned. But it is from aesthetic table reasons and for sorting the combinations in secondary packaging moves, the detergent tablets individually or in several sorted in Fill sacks or bags. For individual application units for washing and cleaning molded article, which are in a sack or pouch, has in Tech nik the term "flow pack" naturalized. Such "flow packs" can then - again preferably sorted - optionally packed in outer packaging, what the compact Offer form of the molded body underlines.  

The sacks or bags made of one layer, which are preferably to be used as a packaging system Mixed or laminated paper or plastic film can be used in many different ways and be designed, for example as an inflated bag without a central seam or as Bags with central seam, which are caused by heat (hot fusion), adhesives or adhesive tapes which are locked. Single-layer bag or sack materials are the known Papers, which may or may not be impregnated, as well as plastic films, which are opposed can also be co-extruded. Plastic films that are within the scope of the present Er can be used as a packaging system are, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düssel Dorf 1988, page 193. Fig. 111 shown there indicates at the same time breakpoints on the water vapor permeability of the materials mentioned.

Combinations particularly preferred within the scope of the present invention as a packaging system, a sack or bag made of single-layer or laminated art material film with a thickness of 10 to 200 microns, preferably from 20 to 100 microns and esp special from 25 to 50 µm.

Although it is possible, wax-coated in addition to the films or papers mentioned Papers in the form of cardboard boxes as a packaging system for washing and cleaning to use medium shaped bodies, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax-coated paper. The The term “packaging system” in the context of the present invention always the primary packaging of the detergent component, detergent together composition or molded article, d. H. the packaging that is directly on the inside with the Detergent component, detergent composition or molded body surface is in contact. There is no requirement for an optional secondary packaging stations, so that all common materials and systems can be used here nen.

As already mentioned above, the detergent components contain Reini detergent compositions or detergent tablets of the inventions combination according to the invention, depending on its intended use  Detergents and cleaning agents in varying amounts. Regardless of the use For the purpose of the agent or molded article, it is preferred according to the invention that the agent (s) or the detergent tablets have a relative equilibrium has / have moisture of less than 30% at 35 ° C.

The relative equilibrium moisture of the detergents or detergents Shaped bodies can be determined using standard methods following investigations the following procedure was chosen: A water permeable 1 liter container with a lid, which has a closable opening for the introduction of samples was carried out with a total of 300 g washing and cleaning medium shaped bodies filled and kept at a constant 23 ° C for 24 h to ensure a uniform Ensure the temperature of the vessel and substance. The water vapor pressure in the room A hygrometer (Hygrotest 6100, Testoterm Ltd., England) can be determined. The water vapor pressure is now measured every 10 minutes, up to two successive values show no deviation (equilibrium moisture speed). The above Hygrometer allows direct display of the recorded values in% relative humidity.

Embodiments of the combination according to the invention are also preferred which the packaging system is designed to be resealable. Also combinations, where the packaging system has a microperforation, can be fiction according to implement with preference.

As mentioned above, detergent components, detergents can be added compositions or detergent tablets for automatic dishwashing produce the inventive method. A cleaning procedure is accordingly ren for cleaning dishes in a dishwasher, characterized in that one or more particulate cleaning agent (s) according to the invention and / or one or more detergent tablets according to the invention by inserting the dosing chamber of the dishwasher and running a washing program, in the course of which opens the dosing chamber and the cleaning agent and / or  the or the shaped body are dissolved, another object of the present Er finding.

Also in the cleaning process according to the invention, one can check the metering chamber spruce and the detergent components or detergents according to the invention compositions or the molded article (s) according to the invention, for example in insert the cutlery basket. It goes without saying that a dosing aid is also used here fe, for example, a basket that is attached to the sink, easily possible Lich. Accordingly, a cleaning process for cleaning dishes in one Dishwasher, characterized in that one or more inven tion moderate (s) detergent and / or one or more inventive moderate detergent tablets with or without dosing aid in the rinse insert the dishwasher and run a washing program, during which the or the cleaning agents and / or the or the shaped body are dissolved, a wide rer 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 example E according to the invention, the commercial rinse aid of the comparative example was added before use by adding Tegopren® 6922 (diquaternary poly (dimethylsiloxane) of the formula III with stearyl residues R, acetations X ^- and a value for n of 30, from Th. Goldschmidt AG) upgraded. The dosage of the rinse aid in both cases was 5 ml per rinse cycle. In Example E according to the invention, 1 gram of Tegopren® 6922 was introduced into the rinse cycle by the rinse aid dosage. A Miele G 590 with 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 using a standard process that in "Methods for determining the cleaning performance of machine dishes dishwashing liquid "(part A: SÖFW-Journal, 124th year 11/98, pages 706 to 713; part B: SÖFW-Journal, 124th year 14/98, pages 1022 to 1034). Be here  also revealed the assessment criteria according to which those listed in the table above led evaluations were made.

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

Claims (23)

1. Use of diquaternary polysiloxanes in automatic dishwashing detergents. 2. Use of diquaternary polysiloxanes in the rinse aid in the machine Wash the dishes. 3. Use according to one of claims 1 or 2, characterized in that one or more diquaternary polysiloxanes of the formula I,
in the Z a quaternized nitrogen center,
R 'and R "independently of one another are a C _1-4 -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 replaced 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,
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,
in the Z the rest
or
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 being} a benzyl radical,
R ^{6 is} an oxygen atom or a group -N (R ⁸ ), where R ^{8 is} a C _1-4 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 replaced 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,
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 ^- an inorganic or organic anion, preferably an acetate, re presented,
be used. 6. Rinse aid for automatic dishwashing, containing diquaternary polysiloxa no 7. rinse aid according to claim 6, characterized in that there are one or more di quaternary polysiloxanes of the formula I,
in the Z a quaternized nitrogen center,
R 'and R "independently of one another are a C _1-4 -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 replaced 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,
contains, rinse aids are preferred which contain one or more diquaternary poly (dimethylsiloxanes) of the formula II,
in the Z the rest
or
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 being} a benzyl radical,
R ^{6 is} an oxygen atom or a group -N (R ⁸ ), where R ^{8 is} a C _1-4 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 replaced 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,
contain and those agents are particularly preferred which contain one or more diquater nary 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 ^- an inorganic or organic anion, preferably an acetate, re presented,
contain. 8. rinse aid according to one of claims 6 or 7, characterized in that it is or 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 contains 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 Ten sid (s), preferably non-ionic surfactant (s) and in particular non-ionic (s) ten  sid (e) from the group of 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% by weight, and contains in particular from 2 to 15% by weight, based in each case on the rinse aid. 10. rinse aid according to one of claims 6 to 9, characterized in that it non-aqueous solvent (s), preferably ethanol, n-propanol, i-propanol, 1- Butanol, 2-butanol, glycol, propanediol, butanediol, glycerin, diglycol, propyl digly kol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, Ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or Bu toxytriglycol, 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
contains, in which each of the radicals R ₁ , R ₂ , R ₃ , R ₄ , R _{5 is} independently selected from H or a C _1-5 alkyl or alkenyl radical and X is a cation. 12. Rinse aid according to one of claims 6 to 11, characterized in that it Acidifying agents, preferably organic acids with particular preference of adipic acid, amidosulfonic acid, succinic acid, citric acid, fumaric acid, mal  Acid, malonic acid, oxalic acid and tartaric acid and mixtures of these acids, ent holds. 13. rinse aid according to one of claims 6 to 12, characterized in that it additionally one or more substances from the groups of soil release polymers, the Dyes and the fragrance contains. 14. Particulate rinse aid for automatic dishwashing, characterized in that it

• a) 0 to 65% by weight of one or more carrier materials,
• b) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,
• c) 0 to 65% by weight of fat (s),
• d) 0 to 50% by weight of further active substances and / or auxiliaries and
• e) 0.1 to 70 wt .-% diquaternary polysiloxanes

contains. 15. Particulate rinse aid according to claim 14, characterized in that it di quaternary polysiloxanes, preferably diquaternary polysiloxanes of the formula I, be 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, based in each case on the particulate clear dishwasher contains. 16. Particulate rinse aid according to one of claims 14 or 15, characterized records that he as ingredient b) one or more substances with a Schmelzbe range between 50 and 100 ° C, preferably between 52.5 and 80 ° C and in particular between 55 and 75 ° C, with paraffin waxes with a melting range of 50 ° C to 65 ° C and / or substances from the group of polyethylene glycols (PEG) and / or Polypropylene glycols (PPG) are preferred coating substances.   17. Particulate rinse aid according to one of claims 14 to 16, characterized is characterized by the fact that, as ingredient d), it additionally contains surfactant (s), preferably nonionic (s) Surfactant (s), particularly preferably those from the group of the alkoxylated alcohols, in Amounts of 5 to 47.5 wt .-%, preferably from 10 to 45 wt .-%, particularly be preferably from 15 to 42.5 wt .-% and in particular from 20 to 40 wt .-%, each be pulled on the particulate rinse aid, contains. 18. Detergent tablets for machine dishwashing, containing framework substances and optionally other ingredients of cleaning agents, characterized records that he diquaternary polysiloxanes, preferably diquaternary polysiloxanes of formula I, particularly preferably diquaternary poly (dimethylsiloxanes) of 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 up to 40 wt .-% and in particular from 5 to 30 wt .-%, each based on the shape body weight, contains. 19. Detergent tablet according to claim 18, characterized in that the di contains quaternary polysiloxanes in a solution-delayed form. 20. Multi-phase detergent tablets for automatic dishwashing, containing builders and optionally further detergent ingredients, characterized in that at least one phase consists of

• a) 0 to 65% by weight of one or more carrier materials,
• b) 30 to 70% by weight of coating substance (s) with a melting point above 50 ° C.,
• c) 0 to 65% by weight of fat (s),
• d) 0 to 50% by weight of further active substances and / or auxiliaries and
• e) 0.1 to 70 wt .-% diquaternary polysiloxanes

consists. 21. Multi-phase detergent tablet according to claim 20, characterized in net that the phases have the form of layers and the molded body 2-, 3- or Is 4-phase.   22. Multi-phase detergent tablet according to claim 20, characterized net that he from a basic molded body, which has a cavity, and a min part of which is contained in the cavity. 23. Multi-phase detergent tablet according to claim 22, characterized in that the part contained in the cavity

• a) 0 to 10% by weight, preferably 0 to 7.5 and in particular 0 to 5% by weight, of one or more carrier materials,
• b) 30 to 70% by weight, preferably 35 to 65% by weight and in particular 40 to 60% by weight of coating substance (s) with a melting point above 50 ° C.,
• c) 0 to 65% by weight, preferably 10 to 60% by weight and in particular 20 to 50% by weight of fat (s),
• d) 0 to 50% by weight, preferably 5 to 45% by weight and in particular 10 to 40% by weight of further active ingredients and / or auxiliaries and
• e) 0.1 to 70 wt .-%, preferably 1 to 50 wt .-% and in particular 5 to 40 wt .-% diquaternary polysiloxanes

consists.