DE10063430A1 - Storage-stable and accurately-dosable detergent components, for use in particulate and multi-phase machine dishwashing agents, comprise a room temperature solid mixture of surfactant(s) and soap(s) - Google Patents

Abstract

A detergent component comprises (in wt.%); (A) surfactant(s) (65-99); and (B) soap(s) (1-35%). An Independent claim is also included for production of the components by melting and mixing the ingredients, followed by cooling and optionally also further processing.

Description

The present invention is in the field of automatic dishwashing detergents for the home standard dishwashers. It concerns detergent components for use in machine dishwashing detergents (MGSM) as well as detergent compositions and cleaning agents Detergent tablets containing such components.

The automatic cleaning of dishes in domestic dishwashers usually includes a pre-rinse, a main rinse and a rinse cycle that of intermediate rinse to be interrupted. On most machines, the pre-rinse cycle is for heavily soiled items Crockery can be switched on, but is only selected by the consumer in exceptional cases, so that in the Most machines have a main wash, an intermediate wash with pure water and a clear rinse cycle. The temperature of the main wash cycle varies depending on the machine Type and program level selection between 40 and 65 ° C. In the rinse aid, a do siertank in the machine added rinse aid, which is usually not the main ingredient African surfactants. Such rinse aids are in liquid form and are in the state of the art Technology broadly described. Your job primarily consists of lime stains and toppings to prevent the cleaned dishes. In addition to water and low-foaming non-ionic surfactants These rinse aids often also contain hydrotopes, pH adjusting agents such as citric acid or scale inhibitors polymers.

The storage tank in the dishwasher must be rinse-aid at regular intervals be filled, whereby one filling is sufficient for 10 to 50 rinse cycles depending on the machine type. Becomes forget to fill up the tank, especially glasses with limescale and deposits unsightly. In the state of the art there are therefore some proposed solutions, a rinse aid to integrate into the detergent for automatic dishwashing.

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

German patent application DE 198 51 426.3 (Henkel KGaA) describes a method for Production of multi-phase detergent tablets, in which a particulate Premix is pressed into moldings which have a trough that later with a se prepared melt from a meltable substance and one or more in it dispersed or suspended active substance (s) is filled. The teaching of this script is also to the Offer form "tablet" bound.

The melt suspensions or emulsions disclosed in the last-mentioned document have al However, an improvement especially when incorporating surfactants as active substances needy long-term stability. The meltable substances should cool down after the emulsi on enclose the active substance and protect against premature release. If the emulsion is too tight sufficiently stable, it partly separates in the molten state before dosing what leads to dosing accuracy. Slightly more stable emulsions can be dosed, but separate partially before solidification, so that the active substance in the cleaning cycle is released early. As a proposed solution, this document discloses the use of various aids medium or stabilizers. If solids are mentioned, however, no statements are made made about their physical properties. The disadvantage is that the addition of auxiliary means etc., the content of active substance in the meltable mass is reduced.

The object of the present invention was to teach the older German patent report DE 198 51 426.3 to further develop and provide long-term stable mixtures that do not tend to separate during dosing and cooling and thus effective and stable cleaners supply agent components. These long-term stable mixtures are said to have an active content Have substance and the detergent components made from them should all known advantages of the controlled release of ingredients, in particular a clear rinsing effect, used for both powder detergents and detergent tablets make cash.

It has now been found that separation-stable detergent components, in particular have meltable mixtures with a high content of active substance produced, if these contain a mixture of surfactants and soaps.

The present invention relates to a detergent component which

• a) 65 to 99% by weight of surfactant (s),  
• b) 1 to 35% by weight of soap (s)

contains.

The term "detergent component" in this context characterizes solidified melts from ingredients a) and b), regardless of their shape. "Detergent components" in the sense of the present application are therefore, for example Dandruff, prills, lozenges, shaped body areas, shaped bodies themselves, etc.

It was found that the mixture of components a) and b) had a firm, elastic, Form gel-like mass. The gel formation temperature is preferably between 30 and 100 ° C, especially between 50 and 75 ° C.

The component gives, especially when incorporated into automatic dishwashing detergents a rinse aid effect. You reach in spite of the multiple water changes in the Household machine similar rinse results as the conventional combinations "Powder + Rinse Aid". After the main wash cycle and the intermediate rinse cycles in the machine remaining amounts of surfactants causes an adequate drainage behavior in the rinse cycle, so that the water draining from the wash ware leaves no stains when drying. The rinse aid does not need when using the agents according to the invention with additional intentionally added Rinse aid to be loaded.

The detergent component according to the invention is preferably solid at room temperature and meltable at higher temperatures. The melting point of such mixtures can be thereby by the type and amount of the individual ingredients, in particular via the melting points and Adjust the amounts of soap (s) and surfactant (s) to the desired value.

The soaps are usually the water-soluble salts of the saturated or unsaturated middle and higher fatty acids, resin acids and naphthenic acids. virtue Fatty acid soaps, w. H. Alkali or ammonium salts, especially the sodium and Potassium salts, used by fatty acids. Soaps of fatty acids, especially caprylic acid, Pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentad canoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, behen acid, palmitoleic acid, oleic acid, erucic acid, hydrogenated erucic acid, linoleic acid, linolenic acid, Elaeostearic acid, arachidonic acid, clupanodonic acid and docosahexaenoic acid and from natural Chen fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures are particularly suitable. The alkali and ammonium soaps of stearin are particularly preferred acid and palmitic acid used, sodium stearate and sodium palmitate being particularly suitable are.  

The soaps are preferably in one in the detergent component according to the invention Amount from 1 to 15 wt .-%, particularly preferably from 8 to 20 wt .-%, based on the finished Detergent component included.

In one possible embodiment there is the detergent component according to the invention only from components a) and b).

In a further embodiment, the melting behavior and the long-term stability of the detergent component according to the invention can be improved by containing a hydrophilizing agent selected from monohydric and polyhydric alcohols and water as further component c). Particularly suitable monohydric alcohols are C ₁ -C ₄ alcohols, such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol and t-butanol. Examples of polyhydric alcohols are glycols, such as ethylene glycol, propylene glycol and butylene glycol, and glycerin.

Component c) is preferably in the cleaning agent component according to the invention in an amount of 5 to 30% by weight, particularly preferably in an amount of 10 to 20% by weight, based on the finished detergent component.

Preferred detergent components contain 65 to 99, preferably 45, as ingredient a) to 94, particularly preferably 50 to 85 wt .-% surfactant (s). All surfactants can the groups of anionic, nonionic, cationic or amphoteric surfactants are, wherein preferred detergent components are characterized in that they as ingredient a) anionic and / or non-ionic surfactant (s), preferably non-ionic (s) Surfactant (s) included.

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

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

As alk (en) yl sulfates, the alkali and in particular the sodium salts of sulfuric acid are the best of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which is biodegradable in the same way as the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and 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 especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic ten side (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular special primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, Alko holethoxylate with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 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 in the 2-position methyl branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fat säuremethylester.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides  can be suitable. The amount of these nonionic surfactants is preferably no longer than that of ethoxylated fatty alcohols, especially not more than half of them.

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

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

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

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

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

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

Particularly preferred are detergent components according to the invention which contain a nonionic contain surfactant that has a melting point above room temperature. As a result, Preferred detergent components are characterized in that they contain a) nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, contain.

Suitable non-ionic surfactants, the melting or softening points in the tempera mentioned have low-foaming nonionic surfactants, which at Room temperature can be solid or highly viscous. Become highly viscous at room temperature Nonionic surfactants used, it is preferred that these have a viscosity above 20 Pas, preferably have above 35 Pas and in particular above 40 Pas. Also non-ionic surfactants that are used in Room temperature waxy consistency are preferred.

Preferred nonionic surfactants to be used as solid at room temperature come from the groups of alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and mixtures thereof Surfactants with structurally more complex tensides such as polyoxypropy len / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.  

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

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

Accordingly, particularly preferred detergent components according to the invention contain, as ingredient a) ethoxylated nonionic surfactant (s) which consists of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the Molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene block copolymer units point. The alcohol or alkylphenol part of such nonionic surfactant molecules is preferred more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight the total molecular weight of such nonionic surfactants. Preferred detergent compo Nenten are characterized in that they are a) ethoxylated and propoxylated Contain nonionic surfactants in which the propylene oxide units in the molecule preferably up to 25 wt .-% up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

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

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

A further preferred detergent components according to the invention contain as an ingredient

• a) nonionic surfactants of the formula
  R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ],
  in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is at least 15.

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

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

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

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

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

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

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

Summarizing the last statements, cleaning agent components according to the invention are preferred which contain, as ingredient a) end-capped poly (oxyalkylated) nonionic surfactants of the formula

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

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

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

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

The detergent components according to the invention can preferably be used as ingredient d) further active substances and / or auxiliary substances from the groups of dyes, fragrances, soil-release Polymers, corrosion inhibitors, enzymes, bleaching agents, bleach activators and complexing agents in Amounts from 0 to 10% by weight, preferably from 0.25 to 7.5% by weight, particularly preferably from 0.5 to 5 wt .-% and in particular from 0.75 to 2.5 wt .-%, contain. Dyes and fragrances like this like the other substances mentioned, the usual ingredients of washing or cleaning means and are described in detail below.

As already mentioned above, through a suitable choice of ingredients a) to d) physical and chemical properties of the detergent composition according to the invention Vary specifically. For example, only ingredients that are used in the Melting temperature of the emulsion are liquid, so it is easy to prepare single-phase mixtures places that are characterized by special storage stability even in the molten state. The addition of solids, such as color pigments or substances with higher enamel score automatically leads to two-phase mixtures, which are also excellent Storage stability and an extremely low tendency to separate.  

At room temperature, the detergent components according to the invention form solidified Mi. representations of the ingredients mentioned, which can take any external form. It it is also possible to apply the mixtures as a melt to carriers and thus carrier materials rial-based detergent components to provide the carrier at room temperature material (ien) and a melt solidified on these carrier materials. As a carrier Materials are all solids that do not soften at the temperature of the melt and which also have a sufficiently large absorption capacity for the melt. Particularly preferred carrier materials are builders, which are described in detail below be.

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

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

melts, mixes, and after cooling, the mixture is processed to give shape.

In this variant of the method, a gel-like mixture is obtained, which processes the shape can be.

The melting of the individual ingredients can be done in all usual mixing devices be performed. The shaping processing step for the mixture obtained is subject to also no procedural restrictions, so that the expert here from the can select a procedure familiar to him. There have been procedures in attempts by the applicant turned out to be preferred, in which the shaping processing by granulating, com compacting, pelleting, extruding or tableting takes place, including processes such as the Verpril len, the pastilling and the scaling by means of cooling rollers are suitable.

In the method according to the invention, the individual ingredients can be used in varying amounts be working.

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

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

injected into a cold gas stream.

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

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

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

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

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

dosed on chilled pastilles.

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

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

The use of cooling rollers is an even more cost-effective variant for producing particulate cleaning agent components of the composition mentioned from melts. Another object of the present invention is therefore a method for producing particulate detergent components, in which a melt is made

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

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

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

Of course, according to the invention it is also possible to use the particulate composition to be pressed into a shaped body or an area thereof. This molded body can be then metered by the consumer, for example, but it can also be in powder form tongues are added. It is also possible to insulate the particulate compositions especially the prills, pastilles or products from the chill roll, as a tablettable premix to use and use in the production of multi-phase moldings. Here delivers the Compression then, for example, multi-layer tablets, one layer of which is together composition of a conventional detergent tablet, the other layer the composition tion of the detergent component according to the invention, which also in this offer form unfolds its advantage.

Multi-phase moldings can also be produced by molding with cavities for example, troughs or through holes, and these cavities are subsequently produced other moldings are filled. In the present case, it has been found that the "basis molded article ", i.e. the tablet having a cavity, the composition of a cleaning agent has medium tablet, while the molded body contained in the cavity has a molded body made of Prills, lozenges, or dandruff is pressed. The adhesion of the two molded bodies to one another can be achieved by gluing the two moldings, but it is also possible to shape body pressed together. Also the nesting, in which the liability by the Geometric design of cavity and filling is possible.

The production process is, for example, the production of the shaped bodies by separate production (Pressing) a base molding A) and a core molding B), which is preferably made of Prills of the detergent components according to the invention is pressed together and the final pressing of both parts is preferred.  

The production of moldings from particulate cleaning agent com components can be made using standard tabletting processes. These are detailed below described.

The moldings can be made in a predetermined spatial shape and size the. Practically all usable configurations come into consideration as spatial form, For example, the training as a board, the rod or bar shape, cubes, cuboids and ent speaking room elements with flat side surfaces and in particular cylindrical Ausge designs with circular or oval cross-section. This final design covers the Presentation form from tablets to compact cylinder pieces with a ratio of height he to diameter above 1.

The molded body produced can assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, five-, seven- and octagonal-prismatic and rhombohedral Forms are preferred. Also completely irregular base areas such as arrow or animal shapes, trees, Clouds etc. can be realized. If the molded article has corners and edges, so they are preferably rounded. As an additional visual differentiation, there is a version Form with rounded corners and chamfered ("chamfered") edges preferred.

The detergent components according to the invention can be sent directly to the consumer Hand be given, so that he dosed them in addition to the detergent as needed. Because of this additional dosing step, however, in addition to the fixed form of supply and Adding to the same dispenser minimizes the advantages over liquid rinse aid. Be It is therefore preferred to make the detergent components according to the invention particulate add machine dishwashing detergents or incorporate them into moldings.

Another object of the present invention is therefore the use of particulate detergent components

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

in detergents for automatic dishwashing.

Another object of the present invention is also a particulate machine dishwashing detergent, containing builders and optionally further detergent ingredients, which contains particulate detergent components, based on their weight,

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

contain.

The ingredients of automatic dishwashing detergents are described below. Partly can also be used as ingredient d) in the detergent components according to the invention be included.

The most important ingredients in automatic dishwashing detergents are builders. In the inventions Detergents according to the invention for machine dishwashing can all be more common builders used in detergents and cleaning agents, in particular So zeolites, silicates, carbonates, organic cobuilders and - if no ecological concerns exist against their use - also the phosphates. The builders listed below are all suitable as carrier materials for the detergent components according to the invention, as stated above.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. 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 disilicate 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 international patent application WO-A-91/08171.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used. which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amor phen sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Cros field) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which was developed by CONDEA 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 less than 10 µm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

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

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

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

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

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

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

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

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

(NaPO ₃ ) ₃ + 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 Mi combinations of these two can be used; also mixtures of sodium tripolyphosphate and natri umkaliumtripolyphosphat or mixtures of potassium tripolyphosphate and sodium potassium tripoly phosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium Umtripolyphosphate can be used according to the invention.

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

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

The acids themselves can also be used. In addition to their builder, the acids possess typically also have the property of an acidifying component and are therefore also used for Setting a lower and milder pH value for detergents or cleaning agents. in particular citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metals tall salts of polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 500 to 70,000 g / mol.

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

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

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As particularly suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acid ren, is generally 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and ins special 30,000 to 40,000 g / mol.

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

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

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

Further preferred copolymers preferably have acrolein and acrylic acid as monomers right / acrylic acid salts or acrolein and vinyl acetate.

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

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

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. The hydrolysis products are preferably of medium molar mass range from 400 to 500000 g / mol. A polysaccharide with a dextrose Equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being one common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Both maltodextrins with a DE between 3 can be used and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are described in detail in the prior art. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine di succinate, are other suitable cobuilders. Here, ethylenediamine-N, N'-disuccinate (EDDS) be preferably used in the form of its sodium or magnesium salts. Also preferred are in in this connection also glycerol disuccinates and glycerol trisuccinates. Suitable use Quantities in formulations containing zeolite and / or silicate are 3 to 15% by weight.

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

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

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

Preferred particulate machine dishwashing detergents according to the invention contain framework substances in amounts of 20 to 80 wt .-%, preferably from 25 to 75 wt .-% and in particular from 30 to 70 wt .-%, each based on the weight of the agent.

In addition to the builders, substances from the groups of surfactants, bleaches, the bleach activators, the enzymes, the polymers as well as the colors and fragrances important content detergent fabrics. Important representatives from the substance classes mentioned described below, with regard to the description of the surfactants on the comments is referred to above.  

Preferred particulate machine dishwashing detergents further contain one or more Substances from the groups of bleaching agents, bleach activators, bleach catalysts, surfactants, corrosis onsinhibitors, polymers, dyes and fragrances, pH adjusting agents, complexing agents and the enzymes.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium percarbonate is of particular importance. Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates such as H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

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

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a solution obtained from sodium carbonate in hydrogen peroxide, but mistakenly referred to as peroxy carbonate hen. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, nevertheless, the historical name "sodium percarbonate" has become established in practice.

The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried at 90 ° C. in fluid bed dryers. The bulk density of the finished product can vary between 800 and 1200 g / l, depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and substances used for coating are widely described in the patent literature. Basically, all commercially available per carbonate types can be used according to the invention, such as are offered by the companies Solvay Interox, Degussa, Kemira or Akzo.

Cleaning agents according to the invention can also contain bleaches from the group of organic Bleach included. Typical organic bleaches are the diacyl peroxides, such as. B. Diben zoylper-oxide. Other typical organic bleaching agents are the peroxy acids, examples of which especially the alkyl peroxy acids and the aryl peroxy acids are mentioned. Preferred representatives  are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxy benzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the ali phatic or substituted aliphatic peroxyacids such as peroxylauric acid, peroxystearic acid right, E-phthalimido-peroxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenz amido-peroxycaproic 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, diperoxybrassylic acid, the diperoxy-phthalic acids, 2- Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used become.

As a bleaching agent in the cleaning agents according to the invention for machine dishwashing substances that release chlorine or bromine can also be used. Among the appropriate ones Chlorine or bromine-releasing materials come, for example, heterocyclic N-bromine and N- Chloramides, for example trichloroisocyanuric acid, tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium in Consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleaches mentioned can also be partially used to achieve "post-bleaching" detergent components according to the invention, where they represent the ingredient d), into the inventions machine dishwashing detergent according to the invention are introduced.

Bleach activators that support the action of the bleaching agents are, for example, compounds which contain one or more N- or O-acyl groups, such as substances from the class of An hydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetyl ethylenediamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhexylenediamine TAHD, however also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and Isa tosic anhydride ISA.

As bleach activators, compounds which are aliphatic under perhydrolysis conditions oxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or result in optionally substituted perbenzoic acid can be used. Substans are suitable zen, the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substi tuated benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, ins special n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid hydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triace tin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-  Methyl sulfate (MMA), and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol respectively their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), Pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, if necessary N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N- Benzoyl. Hydrophilically substituted acylacetals and acyllactams are also considered trains used. Combinations of conventional bleach activators can also be used.

In addition to the conventional bleach activators or in their place, so-called mentioned bleaching catalysts in the detergents for machine dishwashing be prepared. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing ones Tripod ligands and Co, Fe, Cu and Ru amine complexes are available as bleaching catalysts reversible.

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

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

In the cleaning agents according to the invention, the enzymes in particular come from Classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, Amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydro Lases help to remove stains such as stains containing protein, fat or starch kung at. Oxidoreductases can also be used for bleaching. Particularly suitable are from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified  Variants of enzymatic active ingredients obtained. Proteases from subtilisin are preferably Type and in particular proteases obtained from Bacillus lentus. there are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active Enzymes or protease, lipase or lipolytic enzymes, but especially Pro tease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of special interest. Examples of such lipolytically active enzymes are the known ones Cutinases. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes can be absorbed on carriers or embedded in meltable substances, 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 wt .-% %.

Dyes and fragrances can be added to the automatic dishwashing detergents according to the invention are to improve the aesthetic impression of the resulting products and the Ver besides performance, users need a visually and sensory "typical and distinctive" pro to provide products. Individual fragrance compounds can be used as perfume oils or fragrances gene, e.g. B. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and Hydrocarbons are used. Fragrance compounds of the ester type are e.g. B. Ben cyanoacetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbene cylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example se benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, Citral, Citro nellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal the ketones e.g. B. the Jonone, α-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbon substances mainly include terpenes such as limes and pinene. However, Wed are preferred uses different fragrances, which together give an appealing fragrance witness. Such perfume oils can also contain natural fragrance mixtures such as those from plant sources are accessible, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang Ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanu möl as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning agents according to the invention can also be advantageous to apply the fragrances on carriers. As such carrier materials  Cyclodextrins have proven themselves, for example, the cyclodextrin-perfume complexes can also be coated with other auxiliaries. Also an incorporation of the Fragrances as ingredient d) in the detergent components according to the invention are possible and leads to a scent impression when opening the machine.

In order to improve the aesthetic impression of the agents according to the invention, it (or parts of which) are dyed with suitable dyes. Preferred dyes, the selection of which Specialist poses no difficulty, has a high storage stability and is insensitive Compared to the other ingredients of the agent and against light and no pronounced Substantivity towards the substrates to be treated with the agents such as glass, ceramic or Plastic dishes so as not to stain them.

The cleaning agents according to the invention can protect the dishes or the machine Corrosion inhibitors contain, especially silver protection in the field of mechanical Dishwashing have a special meaning. The known substances can be used the state of the art. In general, silver protection agents can be selected from the Group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylami notriazoles and the transition metal salts or complexes are used. Particularly preferred benzotriazole and / or alkylaminotriazole are to be used. One finds in cleaner formulations In addition, agents often containing active chlorine, which clearly corrode the silver surface can reduce. Chlorine-free cleaners especially contain oxygen and nitrogen organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives thereof Classes of compounds. Also salt-like and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. The over are preferred here gear metal salts, which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware the.

The particulate machine dishwashing detergents according to the invention can be the inventive contain appropriate detergent components in varying amounts, the content depending depending on the composition of the detergent components and depending on the desired application success is higher or lower. Preferred particulate machine dishwashing detergents contain the particulate detergent component in amounts of 0.5 to 30 wt .-% before preferably from 1 to 25 wt .-% and in particular from 3 to 15 wt .-%, each based on ge velvet mean.  

The detergent components according to the invention can have a composition be designed so 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 surfactants only in the clear rinse cycle are released and develop their effect here. In addition to this chemical confection Depending on the type of dishwasher, physical assembly is required, so that the rinse aid particles are not pumped out when the water is changed in the machine and so that the rinse aid is no longer available. Domestic dishwashers NEN contain before the drain pump, which the water or the cleaning solution after the pumping individual cleaning cycles out of the machine, a sieve insert that clogs the Should prevent the pump from dirt residues. Crockery heavily contaminated by the consumer rinsed, this strainer must be cleaned regularly, which is due to the easy to Accessibility and removability is easily possible. The cleaning according to the invention Medium components are now preferably designed in terms of their size and shape so that they the sieve insert of the dishwasher even after the cleaning cycle, d. H. after stress due to movement in the machine and the cleaning solution, do not happen. That way ensures that there are detergent components in the dishwasher in the rinse cycle ne, which release the active substance (s) under the influence of the warmer water and bring the desired rinse aid effect. Preferred in the context of the present invention Particulate machine dishwashing detergents are characterized in that the particulate Partial detergent component particle sizes between 1 and 40 mm, preferably between has between 1.5 and 30 mm and in particular between 2 and 20 mm.

In the dishwashing detergents according to the invention, the detergent components can be mixed with the the aforementioned sizes from the matrix of the other particulate ingredients protrude, but the other particles can also have sizes in the range mentioned lie, so that a total of a detergent is formulated, which consists of large detergent and detergent component particles. Especially when the invention Detergent components are colored, for example a red, blue, green or have yellow color, it is for the appearance of the product, i. H. of the entire Reini detergent is advantageous if the detergent components are visibly larger than the dimensions trix from the particles of the other ingredients of the cleaning agent. Here are inventive Particulate automatic dishwashing detergent preferred (without taking into account the part Cheniform detergent component) particle sizes between 100 and 6000 microns, before preferably up to 4500 microns and in particular between 100 and 3000 microns, especially Particle sizes between 300 and 2500 microns and especially between 400 and 2000 microns in particular who are preferred.

If the cleaning agents according to the invention are formulated as a powder mixture, in particular especially with very different sizes of detergent component and detergent matrix  - on the one hand, partial separation occurs when the package is shaken, others on the one hand, the dosage can be different in two successive cleaning cycles, since the consumer does not always necessarily have the same amount of detergent and cleaning agent com component dosed. If desired, technically always the same amount per cleaning cycle to use, this can be done using the packaging of the invention which is familiar to the person skilled in the art Means can be realized in bags made of water-soluble film. Also a particulate machine Les dishwashing detergent, which is characterized in that a dosing unit in a bag water-soluble film is welded, is an object of the present invention.

As a result, the consumer only has one bag which, for example, contains a detergent Contains powder and several optically prominent detergent component particles in the Insert the dosing compartment of his dishwasher. This embodiment of the present The invention is therefore a visually appealing alternative to conventional detergent tablets.

Because the consumer is not just particulate detergents for automatic dishwashing uses, but would also like to use molded articles, these are another object of present invention. For this purpose, the melt from the ingredients a) to d) can be used as a phase formulate a shaped body, for example the shape of a layer, a core-shaped Use etc.

Another object of the present invention is thus a multi-phase detergent tablet for machine dishwashing, containing builders and optionally other detergent ingredients, in which at least one phase

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agents and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

consists.

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

The moldings according to the invention can assume any geometric shape, in particular special concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical drical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octa cathedral, conical, pyramidal, ellipsoid, pentagonal, hexagonal and octagonal prismatic as well as rhombo hedrical forms are preferred. Also completely irregular base areas like arrow or animal shapes, Trees, clouds, etc. can be realized. The shaped bodies according to the invention have corners and edges, they are preferably rounded. As an additional optical differentiation is an embodiment with rounded 33368 00070 552 001000280000000200012000285913325700040 0002010063430 00004 33249eten corners and chamfered ("chamfered") edges vorzugt.

Instead of the layer structure, it is also possible to produce moldings which are the ones according to the invention Include detergent component in the form of other phases. It has proven itself here, Ba Manufacture sisformkörper, which have one or more cavity (s) and the melt the ingredients a) to d) of the detergent component according to the invention into the cavity fill in and freeze there. This manufacturing process gives rise to pulled multiphase detergent tablets, which consist of a base tablet which has a Ka vity, and consist of at least partially contained in the cavity.

The cavity in the pressed part of such shaped bodies according to the invention can have any shape exhibit. You can cut through the molded body, d. H. an opening on different sides, at have for example on the top and bottom of the molded body, but it can also not be through the entire molded body, the opening of only one molded body side is visible. The shape of the cavity can also be freely selected within wide limits. Out For reasons of process economy, there are through holes, the openings of which are adjacent to one another lie opposite surfaces of the molded body, and troughs with an opening on a mold body side proven. In preferred detergent tablets, the cavity has the Form of a continuous hole on the openings of which lie on two opposite ones Molded surfaces are located. The shape of such a through hole can be chosen freely are, wherein shaped bodies are preferred in which the through hole is circular, ellipses shaped, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or eight has angular horizontal sections. Also completely irregular hole shapes like arrow or animal shapes, Trees, clouds, etc. can be realized. As with the moldings in the case of square holes with rounded corners and edges or with rounded corners and chamfered edges preferred.  

The geometric implementation forms mentioned above can be combined with one another as desired combine. Shaped bodies with a rectangular or square base and a circle can be made round holes are produced as well as round shaped bodies with octagonal holes, whereby there are no limits to the variety of possible combinations. For reasons of procedure economy and aesthetic consumer perception are shaped bodies with holes preferred, in which the shaped body base and the hole cross-section have the same geometri form, for example shaped bodies with a square base and centrally integrated finished square hole. Ring moldings are particularly preferred, i. H. circular Shaped body with a circular hole.

If the above Principle of the hole open on two opposite sides of the molded body on one Opening is reduced, mold bodies are obtained. Washing and cleaning according to the invention Molded-body articles in which the cavity has the shape of a depression are also imminent Trains t. As with the "hole moldings", the moldings according to the invention can also be used in this Embodiment take any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal and octagonal-prismatic and rhombohedral shapes preferred are. Completely irregular base areas such as arrow or animal shapes, trees, clouds etc. can also be used will be realized. If the molding has corners and edges, these are preferably abge rounds. An embodiment with rounded corners is an additional optical differentiation and chamfered ("chamfered") edges are preferred.

The shape of the trough can also be chosen freely, preference being given to moldings in which at least one trough a concave, convex, cubic, tetragonal, orthorhombic, cylindrical spherical, cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahe drale, conical, pyramidal, ellipsoid, five-, seven- and octagonal-prismatic as well as rhombo can assume a hedrical form. Also completely irregular trough shapes like arrow or animal shapes, Trees, clouds, etc. can be realized. As with the molded bodies, troughs are included rounded corners and edges or with rounded corners and chamfered edges preferred.

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

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and  
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

consists.

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

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

Analogous statements can also be made for the surfaces, in each case of the base molding or are visible from the detergent component. Here are detergents or cleaning agents Shaped bodies preferred, in which the surface of the cleaning agent com component 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the molded body

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

Of course, detergent tablets according to the invention are also before where the detergent component dissolves later than the base molding. Lei Benefits from this delayed release can be achieved, for example, by that with the help of a more slowly soluble detergent component active substance (s) only in later rinses are released. For example, in automatic dishwashing  can be achieved by slower soluble detergent components that in the rinse cycle additional active substance (s) are available. Through additional substances such as non-ionic Surfactants, acidifying agents, soil-release polymers, etc. can be used to achieve the rinse aid results improve. Incorporation of perfume is also possible without any problems; by its delayed In dishwashers, release can cause the "lye smell" that often occurs when opening the Machine must be eliminated. The ingredients are acidifiers, soil release polymers, etc. then ingredients d) based on the detergent components according to the invention.

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 gdm ^-3, preferably above 1025 gdm ^-3, particularly preferably above 1050 gdm ^-3 and in particular above 1100 gdm ^-3 , are preferred according to the invention.

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

These substances, which are also called "explosives" due to their effect, enlarge their volume in the event of water ingress, with the volume on the one hand increasing (swelling) and the other on the other hand, a pressure can be generated via the release of gases, which the tablet in lets smaller particles disintegrate. Well-known disintegration aids are, for example, carbo nat / citric acid systems, whereby other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrro lidon (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight. % and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case bezo on the molded body weight. Contains only the basic molding disintegration aid, so The information given relates only to the weight of the base molding. At the incorpo ration of disintegration aids in the detergent components according to the invention count those as ingredient d).

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

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

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

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

The detergent tablets according to the invention can moreover both in the basic form body as well as in the detergent component contain a gas-developing shower system. The gas-evolving shower system can consist of a single substance that is in contact releases a gas with water. Among these compounds is magnesium peroxide in particular to name, which releases oxygen on contact with water. This is usually gas-free zende bubble system, however, in turn, from at least two components, which together under React gas formation. While here a multitude of systems is conceivable and executable, the For example, release nitrogen, oxygen or hydrogen, that will be in the Invention bubble system used in accordance with the detergent tablets used, both based on let you choose more economical and ecological considerations. Preferred brew Systems consist of alkali metal carbonate and / or bicarbonate as well as an acidification agent that is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution Zen.

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

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

As acidifying agents that release carbon dioxide from the alkali salts in aqueous solution for example boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, organic acidification is preferred agent used, the citric acid being a particularly preferred acidifying agent.  

However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. From this group tartaric acid, succinic acid, malonic acid, adipic acid are preferred right, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as ami Dosulfonic acid can also be used. Commercially available and as an acidifier in Within the scope of the present invention, Sokalan® DCS (Warenzei BASF), a mixture of succinic acid (max. 31 wt.%), glutaric acid (max. 50 wt. %) and adipic acid (max. 33% by weight).

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

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

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

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

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

The relative equilibrium humidity of 85% at 23 ° C can be found, for example, in the laboratory moisture control to +/- 2% r. Adjust L. exactly. Also about ge saturated solutions of certain salts form in closed systems at a given temperature constant and well-defined relative air humidity, which is based on the phase Balance between partial pressure of water, saturated solution and soil body.

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

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

The packaging system of the combination according to the invention encloses, depending on the design form of the invention a certain amount of detergent component according to the invention, a certain amount of a particulate detergent composition or one or  several detergent tablets. It is preferred according to the invention ent to design neither a shaped body so that it is an application unit of the washing and Detergent includes, and to package this molded article individually, or the number of form body to pack in a packaging unit, which in total comprises an application unit. With a nominal dosage of 80 g of detergent and cleaning agent, it is therefore possible according to the invention Lich to produce a 80 g detergent tablet and individually pack, but it is also possible according to the invention, two 40 g washing and cleaning Packing agent in a package to form a combination according to the invention nation to arrive. This principle can of course be extended so that the invention Combinations also three, four, five or even more detergent tablets in can contain a packaging unit. Of course, two or more molded articles have different compositions in one package. That way it is possible to spatially separate certain components from each other, for example, stability to avoid problems.

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

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

The sacks or bags made of single-layer or laminated paper or plastic film, which are preferably to be used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam, which is caused by heat (hot fusion), adhesives or adhesive tapes be closed. The known papers, which can optionally be impregnated, as well as plastic films, which can optionally be coextruded, are layered bag or sack materials. Plastic films that can be used as a packaging system in the context of the present invention are given, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf, 19881 page 193. Fig. 111 shown there also provides information on the water vapor permeability of the materials mentioned.

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

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

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

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

Embodiments of the combination according to the invention are also preferred, in which the Packaging system is designed to be resealable. Combinations in which the ver packaging system has a microperforation, can be realized according to the invention with preference ren.

As mentioned above, detergent components, detergents can be combined settlements or detergent tablets for automatic dishwashing according to the inventions produce the method according to the invention. Accordingly, a cleaning process is for cleaning of dishes in a dishwasher, characterized in that one or more Particulate detergent according to the invention and / or one or more inventions the detergent tablets according to the invention the dosing chamber of the dishwasher inserted and a rinsing program can run, in the course of which the dosing chamber opens and the detergent or detergents and / or the molded article or articles are dissolved, another Subject of the present invention.

The metering chamber can also be dispensed with in the cleaning process according to the invention and the detergent components or detergent composition according to the invention tongues or the shaped body or bodies according to the invention for example in the cutlery basket Insert. Of course, the use of a dosing aid, for example one, is also here Basket, which is attached in the sink, easily possible. Accordingly, a Rei cleaning process for cleaning dishes in a dishwasher, characterized records that one or more particulate detergent according to the invention and / or one or more shaped tablets according to the invention or in the dishwasher's washing compartment without a dosing aid and run a washing program can, in the course of which the cleaning agent or detergents and / or the molded body or the dissolved are another object of the present invention.

Examples

Compositions (moldings) of the following composition [% by weight] were produced:

For this purpose, the individual components were heated to 85 ° C. and stirred until a homogeneous Ge was mixed. After cooling, the compositions showed a firm consistency, the composition V2 was stronger (had a greater hardness). The melted Masses were poured into tablets that had a trough-shaped cavity. It was in a household dishwasher, cleaning cycles at 50 ° C and 65 ° C. At a Dishwashing at 50 ° C detached part of the molded body according to the invention in the main line and a part in the rinse aid. When washing dishes at 65 ° C, the ge Entire moldings already released in the main cleaning cycle.

Claims (35)

1. detergent component that

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s)

contains. 2. Detergent component according to claim 1, characterized in that it is in space temperature-resistant and meltable at higher temperatures. 3. Detergent component according to one of claims 1 or 2, characterized in that that the soaps are the water-soluble salts of the saturated or unsaturated medium and high Other fatty acids, resin acids and naphthenic acids can be used. 4. detergent component according to claim 3, characterized in that the soaps are selected from the alkali or ammonium salts, in particular the sodium and potassium salts, of C ₈ -C ₂₂ fatty acids, preferably sodium stearate and sodium palmitate, 5. Detergent component according to one of claims 1 to 4, characterized in that the soap in an amount of 1 to 15 wt .-%, particularly preferably from 8 to 20 wt .-%, be moved to the finished detergent component, are included. 6. Detergent component according to one of claims 1 to 5, characterized in that a hydrophilizing agent selected from monohydric and polyhydric alcohols and water, in particular from C ₁ -C ₄ alcohols, such as methanol, ethanol, n-propanol, as further component c) , iso-propanol, n-butanol, iso-butanol and t-butanol, polyhydric alcohols, such as glycols, in particular ethylene glycol, propylene glycol and butylene glycol, and glycerol and any mixtures of the foregoing. 7. Detergent component according to claim 6, characterized in that the component c) in an amount of 5 to 30% by weight, preferably 10 to 20% by weight, based on the fer term detergent component is included. 8. Detergent component according to one of claims 1 to 7, characterized in that it as ingredient a) anionic and / or nonionic surfactant (s), preferably nonio niche surfactant (s). 9. Detergent component according to one of claims 1 to 8, characterized in that it as ingredient a) nonionic surfactant (s) with a melting point above 20 ° C,  preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular which contains between 26, 6 and 43, 3 ° C. 10. detergent component according to any one of claims 1 to 9, characterized in that it contains as ingredient a) ethoxylated (s) nonionic surfactant (s), the / which from C _6-20 -monohydroxyalkanols or C _6-20 -alkylphenols or C _{16- 20} fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was obtained. 11. Detergent component according to one of claims 1 to 10, characterized in that that they contain as ingredient a) ethoxylated and propoxylated nonionic surfactants, in which the Propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and esp make up in particular up to 15% by weight of the total molar mass of the nonionic surfactant, contains. 12. Detergent component according to one of claims 1 to 11, characterized in that it contains as the ingredient a) nonionic surfactants of the formula
R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ]
contains, in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1.5 and y stands for a value of at least 15. 13. Detergent component according to one of claims 1 to 10, characterized in that it contains, as ingredient a) end-capped poly (oxyalkylated) nonionic surfactants of the formula
R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²
contains in which R ¹ and R ^{2 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, with surfactants of the type
R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²
in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred. 14. Detergent component according to one of claims 1 to 13, characterized in that they contain, as ingredient d), further active substances and / or auxiliary substances from the groups of dyes, Fragrances, soil-release polymers, corrosion inhibitors, enzymes, bleaches, bleach activators ren and complexing agents in amounts of 0 to 10 wt .-%, preferably from 0.25 to 7.5 wt .-%, particularly preferably from 0.5 to 5% by weight and in particular from 0.75 to 2.5% by weight %, contains. 15. Detergent component according to one of claims 1 to 14, characterized by egg NEN melting point between 50 and 80 ° C, preferably between 52.5 and 75 ° C and esp especially between 55 and 65 ° C. 16. A process for the production of particulate detergent components, characterized in that

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

melts, mixes, and after cooling, the mixture is processed to give shape. 17. The method according to claim 16, characterized in that the shaping processing by granulating, compacting, pelleting, extruding or tableting. 18. Process for the production of prilled detergent components, characterized in that a melt is formed

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

injected into a cold gas stream. 19. Process for the preparation of detergent components, characterized in that a melt is produced

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

dosed on chilled pastilles. 20. A process for the production of particulate detergent components, characterized in that a melt from

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

applied or sprayed onto a chill roll, scraped off the solidified melt and, if necessary, shredded. 21. Use of particulate detergent components

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

in detergents for automatic dishwashing. 22. Particulate machine dishwashing detergent containing builders and optionally further detergent ingredients, characterized in that it contains particulate cleaning agent components based on their weight,

• a) 10 to 865 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

contain. 23. Particulate machine dishwashing detergent according to claim 22, characterized in that that there are builders in amounts of 20 to 80% by weight, preferably 25 to 75% by weight and in particular from 30 to 70 wt .-%, each based on the weight of the agent. 24. Particulate dishwasher detergent according to one of claims 22 or 23, since characterized in that it still contains one or more substances from the groups of Bleaching agents, bleach activators, bleaching catalysts, surfactants, corrosion inhibitors, polymers, Contains dyes and fragrances, pH regulators, complexing agents and the enzymes. 25. Particulate dishwasher detergent according to one of claims 22 to 24, because characterized in that it contains the particulate detergent component in amounts of  0.5 to 30% by weight, preferably 1 to 25% by weight and in particular 3 to 15% by weight %, each based on the total mean. 26. Particulate dishwasher detergent according to one of claims 22 to 25, since characterized in that the particulate detergent component has particle sizes between 1 and 40 mm, preferably between 1.5 and 30 mm and in particular between 2 and has 20 mm. 27. Particulate dishwasher detergent according to one of claims 22 to 26, since characterized in that it (without taking into account the particulate detergent component) particle sizes between 100 and 3000 microns, preferably between 300 and 2500 µm and in particular between 400 and 2000 µm. 28. Particulate dishwasher detergent according to one of claims 22 to 27, since characterized in that a dosing unit is inserted into a bag made of water-soluble film welds present. 29. Multi-phase detergent tablets for automatic dishwashing, containing builders and optionally further detergent ingredients, characterized in that at least one phase consists of

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

consists. 30. Multi-phase detergent tablet according to claim 29, characterized in that the phases have the form of layers and the shaped body is 2-, 3- or 4-phase. 31. Multi-phase detergent tablet according to claim 29, characterized in that it consists of a base molding, which has a cavity, and an at least partially part contained in the cavity. 32. Multi-phase detergent tablet according to claim 31, characterized in that the part contained in the cavity

• a) 65 to 99% by weight of surfactant (s),
• b) 1 to 35% by weight of soap (s),
• c) 0 to 30 wt .-% hydrophilizing agent and
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

consists. 33. Combination of (a) particulate cleaning agent (s) according to one of claims 22 to 28 and / or (a) detergent or cleaning product body (s) according to one of claims 29 to 32 and one of the cleaning agent and / or the or Packaging system containing detergent and cleaning product tablets, characterized in that the packaging system has a moisture vapor permeability rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is at 23 ° C and a relative equilibrium moisture content of 85% is stored. 34. Cleaning process for cleaning dishes in a dishwasher, thereby characterized in that one or more particulate detergent (s) according to a of claims 22 to 28 and / or one or more detergent tablets per according to one of claims 29 to 32 in the dosing chamber of the dishwasher and a rinsing program can run, in the course of which the metering chamber opens and the or the cleaning agents and / or the shaped body or bodies are dissolved. 35. Cleaning process for cleaning dishes in a dishwasher, thereby characterized in that one or more particulate detergent (s) according to a of claims 22 to 28 and / or one or more detergent tablets per according to one of claims 29 to 32 with or without metering aid in the wash cabinet of the wash machine and runs a washing program, in the course of which the Reini agent and / or the shaped body or bodies are dissolved.