WO2001016283A1 - Detergent constituent - Google Patents

Abstract

The invention relates to long-term stable mixtures which do not tend to separate, thus providing effective and stable detergent constituents. Said mixtures contain between 10 and 90 wt. % of surfactant(s), between 10 and 90 wt. % of fatty substance(s), between 0 and 70 wt. % of soluble substance(s), having a melting-point above 30 DEG C and between 0 and 15 wt. % of additional active ingredients and/or auxiliary agents.

Description

 "Detergent component"

The present invention is in the field of machine dishwashing detergents for household dishwashers. It relates to detergent components for use in machine dishwashing detergents (MGSM) as well as detergent compositions and detergent tablets containing such components

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

The storage tank in the dishwasher must be filled with rinse aid at regular intervals, with one filling sufficient for 10 to 50 rinse cycles, depending on the machine type. If you forget to fill up the tank, glasses in particular become unsightly due to limescale and deposits. In the prior art there are therefore some proposed solutions for integrating a rinse aid into the detergent for machine dishwashing. For example, European patent application EP-A-0 851 024 (Unilever) describes two-layer detergent tablets, the first layer of which contains peroxy bleach, builder and enzyme, while the second layer contains acidifying agents and a continuous medium with a melting point between 55 and 70 ° C. and scale inhibitors contains. Due to the high-melting continuous medium, the acid (s) and deposit inhibitor (s) should be released with a delay and produce a rinse aid effect. Powder-form machine dishwashing detergents or surfactant-containing rinse aid systems are not mentioned in this document.

The older German patent application DE 198 51 426.3 (Henkel KGaA) describes a process for the production of multiphase detergent tablets, in which a particulate premix is pressed to give moldings which have a trough which is later made with a separately produced melt from a meltable substance and one or more active substance (s) dispersed or suspended in it. The teaching of this document is also tied to the "tablet" offer.

The melt suspensions or emulsions disclosed in the last-mentioned document, however, have long-term stability in need of improvement, especially when incorporating surfactants as active substances. After the emulsion has cooled, the meltable substances should enclose the active substance and protect against premature release. If the emulsion is insufficiently stable, it partially separates in the molten state before metering, which leads to metering accuracy. Slightly more stable emulsions can be dosed, but they partially separate before solidification, so that the active substance is released early in the cleaning cycle.

The object of the present invention was to provide mixtures which are stable over the long term and which do not tend to separate during metering and cooling and thus provide effective and stable detergent components. If possible, the addition of stabilizers should be avoided. A single-phase formulation which can no longer tend to separate should be provided in a particularly preferred manner. These long-term stable mixtures and the detergent components made from them should all the known advantages of controlled Release of ingredients, especially a rinse aid, can be used both for powder-form detergents and for detergent tablets.

It has now been found that stable melts can be produced from meltable substances with melting points above 30 ° C., surfactant (s) and optionally further ingredients such as emulsifiers, colorants and fragrances, etc., if these mixtures contain at least 10% by weight of fatty substances ) contain. Depending on the type of surfactants used and the other active and auxiliary substances, these can also be produced in one phase.

The melting point of such mixtures can be specifically adjusted to the desired value by the type and amount of the individual ingredients, in particular via the melting points and amounts of meltable substance (s) and fatty substances. Mixtures which are stable to separation are present above the melting point, and mixtures of any shape which are solidified below the melting point and which are referred to as detergent components in the context of the present application.

The present invention relates to a detergent component which contains a) 10 to 90% by weight of surfactant (s), b) 10 to 90% by weight of fatty substances), c) 0 to 70% by weight of meltable substance (s) a melting point above 30 ° C and d) contains 0 to 15 wt .-% of other active ingredients and / or auxiliaries.

The term “detergent component” in the context of the present application denotes solidified mixtures of the ingredients a) to d), regardless of their shape. “Detergent component” in the sense of the present application is therefore, for example, dandruff, prills, lozenges, shaped body areas, shaped bodies per se etc.. Preferred detergent components contain 15 to 80, preferably 20 to 70, particularly preferably 25 to 60 and in particular 30 to 50% by weight of surfactant (s) as ingredient a). All surfactants from the groups of anionic, nonionic, cationic or amphoteric surfactants can be used, preferred detergent components being characterized in that they contain, as ingredient a) anionic and / or nonionic surfactant (s), preferably nonionic surfactant (s).

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C 9 ₁₃ - alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from _2- Cι ι ₈ -Monoolefιnen with terminal or internal double bond by sulfonation with Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _2- i ₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

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

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the -C ₂ -C ₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol. Lauryl, myristyl, cetyl or stearyl alcohol or the Cιo-C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which is biodegradable in the same way as the adequate compounds based on oleochemical raw materials. For reasons of washing technology, the C 1 -C ₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₄ -C ₅ alkyl sulfates are preferred. 2,3-Alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9. ₁₁ alcohols with an average of 3.5 moles of ethylene oxide (EO) or

with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8- ι ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) yl gemstemic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, Cι ι _2- alcohols with 3 EO or 4 EO, C ₉ .ιι-Al ohol with 7 EO, Cι ι _{3- 5} alcohols containing 3 EO, 5 EO, 7 EO or 8 EO , _C12 - ₁₈ - alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of _2- Cι ι ₄ alcohol containing 3 EO and C12-1 ₈ - alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x. indicating the distribution of monoglycosides and oligoglycosides is any number between 1 and 10; x is preferably 1.2 to 1.4. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.

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

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

R ^]

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

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ^ 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)

R -OR ² R-CO-N- [Z] (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 an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C - alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical ,

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

Low-foaming nonionic surfactants are used as preferred surfactants. The detergent components according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, Cπ-ir alcohols with 3 EO or 4 EO, Cg.n alcohol with 7 EO, C1 ₃ . ₁₅ - alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cι _2- ι ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C1 ₂ - 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Cleaning agent components according to the invention which contain a nonionic surfactant which has a melting point above room temperature are particularly preferred. Accordingly, preferred detergent components are characterized in that they contain, 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 between 26. 6 and 43.3 ° C included.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

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

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

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C | _6-2 alcohol), preferably a Cι ₈ alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 mole Ethylene oxide obtained. Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

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

Further nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of a returned block copolymers of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylol propane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

A further preferred cleaning agent components according to the invention contain non-ionic surfactants of the formula as ingredient a)

RO [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ θ] _y [CH ₂ CH (OH) R ² ],

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

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

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

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

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

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

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

1 ") ~. In the last-mentioned formula, R, R and R 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 represents} H and x assumes values from 6 to 15.

If the latter statements are summarized, cleaning agent components according to the invention are preferred which contain end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] [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 0 [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.

The detergent components according to the invention contain one or more fatty substances as ingredient b), preferred detergent components being characterized in that they contain 12.5 to 85, preferably 15 to 80, particularly preferably 17.5 to 75 and in particular 20 to 70% by weight as ingredient b) .-% fat).

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

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

The fatty alcohols that can be obtained from native fats and oils are, for example, alcohols 1-hexanol (capro alcohol), 1-heptanol (enant alcohol), 1-octanol (caprylic alcohol), 1-nonanol (pelargon alcohol), 1-decanol (capric alcohol), 1 -Undecanol, 10- undecen-1 -ol, 1-dodecanol (lauryl alcohol), 1-tridecanol, 1 -Tetradecanol (myristylal- alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), 9-cis-octadecen-l-ol (oleyl alcohol), 9-trans-octadecen-l-ol (erucylal- alcohol), 9-cis-octadecene-l, 12-diol (ricinol alcohol), all-cis-9,12-octadecadien-l-ol (linoleyl alcohol), all-cis-9,12,15-octadecatriene-l -ol (linolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 9-cis-eicosen-l-ol (gadoleyl alcohol),

5,8,11,14-eicosatetraen-l-ol, 1-heneicosanol, 1-docosanol (behenyl alcohol), 1-3-cis-docosen-l-ol (erucyl alcohol), 1-3-trans-docosen-l- ol (brassidyl alcohol) and mixtures of these alcohols. The invention also Guerbet alcohols and oxo alcohols, for example, Cι -ι _5-oxo alcohols or mixtures of C ₂ -i ₈ alcohols with C i ₂ - ₁₄ - alcohols easily be used as fatty substances. Of course, it can also alcohol mixtures are used, for example those as the polymerization by ethylene produced by the Ziegler-Ci6 ι ₈ - alcohols. Specific examples of alcohols which can be used as component b) are the alcohols already mentioned, and lauryl alcohol, palmityl and stearyl alcohol and mixtures thereof.

Particularly preferred detergent _components according to the invention contain, as ingredient b), one or more Cio-fatty alcohols, preferably Ci _2-24 fatty alcohols, with particular preference for 1-hexadecanol, 1-Octadecanol, 9-cis-octadecen-l-ol, all-cis- 9,12-octadecadien-l-ol, all-cis-9,12,15-octadecatrien-l-ol, 1-docosanol and mixtures thereof.

Fatty acids can also be used as ingredient b). Technically, most of these are obtained from native fats and oils by hydrolysis. While the alkaline saponification which was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as fatty substances in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. In the context of the present compound, preference is given to Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (pal mitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid), triacotanoic acid (melissic acid) and the unsaturated secies 9c-hexadecenoic acid (6-mitocenoic acid) (palmit ), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadolate acid ). Of course, tridecanoic acid, pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid can also be used. For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, as are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, wt .-% 6 Cι _0, 48 wt .-% C, _2, 18 wt .-% _{C) 4} 10 wt .-% C, ₆ , 2 wt% cis, 8 wt% cig, 1 wt% C | ₈ -). Palmkemölfettsäure (about 4 wt .-% C _8, 5 wt .-% C, _0, 50 wt .-% C, _2, 15 wt .-% C _14, 7 wt .-% C, _6, 2 wt. -% C, ₈ , 15 wt .-% C ₁₈ -, 1 wt .-% cis), tallow fatty acid (approx. 3 wt .-% C _i4 , 26 wt .-% Cι ₆ , 2 wt .-% Cι ₆ , 2 wt .-% Cπ, 17 wt .-% cis, 44 wt .-% cis, 3 wt .-% Cι ₈ -, 1 wt .-% C, ₈ -), hardened tallow fatty acid (approx. 2 wt .-% C ₁₄ , 28 wt .-% Cι ₆ , 2 wt .-% C _{] 7} , 63 wt .-% C _{) 8} , 1 wt .-% Cι ₈ ), technical oleic acid (about 1 wt .-% % C ₂ , 3 wt .-% C ₁₄ , 5 wt .-% C ₆ , 6 wt .-% C ₁₆ -, 1 wt .-% C ₁₇ , 2 wt .-% Cis, 70 wt .-% Cι ₈ -, 10 wt .-% Cι ₈ -, 0.5 wt .-% C ₁₈ ^{■ ••} ), technical palmitin / stearic acid (approx. 1 wt .-% C12, 2 wt .-% Cι, 45 wt. -% C ₆ , 2 wt .-% C ₁₇ , 47 wt .-% cis, 1 wt .-% Cι ₈ ) and soybean oil fatty acid (about 2 wt .-% C ₁₄ , 15 wt .-% Cι ₆ , 5th % By weight Cis, 25% by weight Cι ₈ -, 45% by weight C _{) 8} -, 7% by weight C, ₈ -).

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

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

As a third ingredient, the detergent components according to the invention contain one or more meltable substance (s) with a melting point above 30 ° C., preferred detergent components being characterized in that they contain 0 to 65, preferably 0 to 60, particularly preferably 0 to 60 as ingredient c) Contain 55 and in particular 0 to 50 wt .-% meltable substance (s).

Various requirements are placed on the meltable substances that are used in the detergent components according to the invention, which relate on the one hand to the melting or solidification behavior, but on the other hand also to the material properties of the melt in the solidified state, ie in the detergent components according to the invention. Since the detergent component is to be permanently protected against environmental influences during transport or storage, the fusible substance must have a high stability against, for example, shock loads occurring during packaging or transport. The fusible substance should therefore either have at least partially elastic or at least plastic properties in order to react to an impact load that occurs due to elastic or plastic deformation and not to break. The meltable substance should have a melting range (solidification range) in such a temperature range at which other ingredients of the detergent components according to the invention are not exposed to excessive thermal stress. On the other hand, however, the melting range must be sufficiently high to still provide effective protection for the active substances at at least a slightly elevated temperature. According to the invention, the fusible substances have a melting point above 30 ° C., preference being given to detergent components which have only fusible substances with melting points above 40 ° C., preferably above 45 ° C. and in particular above 50 ° C. Particularly preferred detergent components contain, as ingredient c), one or more substances with a melting range between 30 and 100 ° C., preferably between 40 and 80 ° C. and in particular between 50 and 75 ° C.

It has proven to be advantageous if the meltable substance does not have a sharply defined melting point, as usually occurs with pure, crystalline substances, but instead has a melting range that may include several degrees Celsius.

The meltable substance preferably has a melting range which is between approximately 52.5 ° C. and approximately 80 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. The width of the melting range is preferably at least 1 ° C., preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. “Waxing” is understood to mean a number of natural or artificially obtained substances which generally melt above 50 ° C. without decomposition and which are relatively low-viscosity and not stringy just above the melting point. They have a strongly temperature-dependent consistency and solubility.

The waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes. Natural waxes include, for example, vegetable waxes such as candelilla wax, camauba wax, japan wax, esparto grass wax, cork wax, guaruma wax. Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat. Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

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

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of substances which meet the stated softening point requirements can also be used as ingredient c). Higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll 66 (Bayer AG), have proven to be suitable synthetic compounds, for example. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea).

The ingredient c) contained in the detergent components according to the invention preferably contains a proportion of paraffin wax. This means that at least 10% by weight of the total meltable substances contained, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total amount of meltable substance) of approximately 12.5% by weight, approximately 15% by weight or approximately 20% by weight are particularly suitable, even higher proportions of, for example, more than 30% by weight. can be particularly preferred. In a special embodiment of the invention, the total amount of meltable substance used consists exclusively of paraffin wax.

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

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

Preferred cleaning agent components contain as ingredient c) at least one paraffin wax with a melting range from 30 ° C. to 65 ° C.

Preferably, the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally about 10 to about 30 ° C.) is as high as possible. The more solid wax components present in a wax at room temperature, the more useful it is within the scope of the present invention. With an increasing proportion of solid wax components, the resistance of the cleaning agent component to impacts or friction on other surfaces increases, which leads to a longer-lasting protection of the active substances. High proportions of oils or liquid wax components can lead to weakening, which opens pores and the active substances are exposed to the environmental influences mentioned at the beginning.

In addition to paraffin, the meltable substance can also contain one or more of the waxes or wax-like substances mentioned above. Preferably, the mixture forming the fusible substance should be such that the detergent components are at least largely water-insoluble. The solubility in water should be at a Temperature of about 30 ° C do not exceed about 10 mg / 1 and are preferably below 5 mg / 1.

In any case, however, the material should preferably have the lowest possible solubility in water, even in water at an elevated temperature, in order to largely avoid a temperature-independent release of the active substances.

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

However, the principle mentioned can also be reversed to the effect that the active substance (s) are not released from the material but are released faster. This can be achieved in a simple manner by using dissolving retarders, rather than dissolving accelerators, as meltable substances, so that the solidified melt does not dissolve slowly, but rather quickly. In contrast to the poorly water-soluble dissolution retarders described above, preferred dissolution accelerators are readily water-soluble. The water solubility of the dissolving accelerators can be increased significantly by certain additives, for example by incorporating easily soluble salts or effervescent systems. Such accelerated, meltable substances (with or without the addition of other solubility improvers) lead to a rapid release of the enclosed active substances at the beginning of the cleaning cycle.

The above-mentioned synthetic waxes from the group of polyethylene glycols and polypropylene glycols are particularly suitable as dissolving accelerators, ie fusible substances for the accelerated release of the active substances from the cleaning agent components, so that preferred cleaning agent components as ingredient c) have at least least contain a substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG).

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are polymers of ethylene glycol which have the general formula III

H- (O-CH ₂ -CH ₂ ) _n -OH (III)

are sufficient, where n can have values between 1 (ethylene glycol) and over 100,000. Decisive in the evaluation of whether a polyethylene glycol can be used according to the invention. is the physical state of the PEG, ie the melting point of the PEG must be above 50 ° C, so that the monomer (ethylene glycol) and the lower oligomers with n = 2 to about 16 cannot be used, since they have a melting point below Have 50 ° C. The polyethylene glycols with higher molecular weights are polymolecular, ie they consist of groups of macromolecules with different molecular weights. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. According to this nomenclature, the technically customary polyethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 can preferably be used in the context of the present invention. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and directly after the hyphen is followed by a number which corresponds to the number n in the above-mentioned formula III. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient DIC tionary and Handbook, ^5th Edition. The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-32, PEG-40, PEG-55, PEG-60th PEG-75, PEG-100, PEG-150 and PEG-180 can preferably be used according to the invention.

Commercially available polyethylene glycols, for example, under the trade names Carbowax ^s> PEG 540 (Union Carbide), Emkapol * 6000 (ICI Americas), Lipoxol ^® 3000 MED (HÜLS America), Polyglycol ^® E-3350 (Dow Chemical), Lutrol ^® E4000 (BASF) and the corresponding trade names with higher numbers.

Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula IV

H- (O-CH-CH ₂ ) _n -OH (IV)

CH ₃

are sufficient, where n values can be between 1 (propylene glycol) and approx. 1000. Similar to the PEG described above, the assessment of whether a polypropylene glycol can be used according to the invention depends on the physical state of the PPG, i.e. the melting point of the PPG must be above 50 ° C, so that the monomer (propylene glycol) and the lower oligomers with n = 2 to approx. 15 cannot be used, since they have a melting point below 30 ° C.

In addition to the PEG and PPG, which can preferably be used as solution-accelerated meltable substances, other substances can of course also be used, provided they have a sufficiently high water solubility and a melting point above 30 ° C.

The detergent components according to the invention can preferably contain, as ingredient d), further active ingredients and / or auxiliaries from the groups of dyes, fragrances, anti-settling agents, floating agents, anti-floating agents, thixotropic agents and dispersing agents in amounts of 0 to 10% by weight, preferably of 0. 25 to 7.5 wt .-%, particularly preferably from 0.5 to 5 wt .-% and in particular from 0.75 to 2.5 wt .-%, contain. While dyes and fragrances are described below as the usual ingredients of detergents or cleaning agents, the ingredients which are specific for the cleaning agent components according to the invention are described below. At extraordinarily low temperatures, for example at temperatures below 0 ° C., the cleaning agent component according to the invention can break under impact or friction. In order to improve the stability at such low temperatures, additives can optionally be added to the meltable substances. Suitable additives must be able to be mixed completely with the molten wax, must not significantly change the melting range of the meltable substances, must improve the elasticity of the detergent component at low temperatures, must not generally increase the permeability of the detergent component to water or moisture and must not increase the viscosity of the Do not increase the melt to such an extent that processing becomes difficult or even impossible. Suitable additives which reduce the brittleness of a material consisting essentially of paraffin at low temperatures are, for example, EVA copolymers, hydrogenated resin acid methyl ester, polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.

It may also be advantageous to add further additives to the meltable substance, for example to prevent the mixture from prematurely separating. The anti-settling agents that can be used for this purpose, which are also referred to as floating agents, are known from the prior art, for example from the manufacture of lacquers and printing inks. In order to avoid sedimentation and concentration differences of the substances during the transition from the plastic solidification area to the solid, there are, for example, surface-active substances, waxes dispersed in solvents, montmorillonites, organically modified bentonites, (hydrogenated) castor oil derivatives, soy lecithin, ethyl cellulose, low molecular weight polyamides, metal stearates, calcium soaps or hydrophobized silicas. Other substances which bring about the effects mentioned come from the groups of anti-floating agents and thixotropic agents and can be chemically used as silicone oils (dimethylpolysiloxanes, methylphenylpolysiloxanes, polyether-modified methylalkylpolysiloxanes), oligomeric titanates and silanes, polyamines, salts from long-chain polyamines and polycarboxylic acids, Amine-amide-functional polyesters or amine-amide-functional polyacrylates are referred to.

Additives from the substance classes mentioned are commercially available in a wide variety. Commercial products that are used in the process according to the invention Aerosil ^® 200 (pyrogenic silica, Degussa), Bentone ^® SD-1, SD-2, 34, 52 and 57 (bentonite, Rheox), Bentone * SD-3, 27 and 38 (e.g. Hectorite, Rheox), Tixogel ^® EZ 100 or VP-A (organically modified smectite, Südchemie), Tixogel ^® VG, VP and VZ (montmorillonite, Südchemie loaded with QAV), Disperbyk ^® 161 (block copolymer, Byk-Chemie), Borchigen ^® ND (sulfo group-free ion exchanger, Borchers), Ser-Ad ^® FA 601 (servo), brine ^? (aromatic ethoxylate, ICI), Surfynol ^® types (Air Products), Tamol ^® and Triton ⁵ types (Rohm & Haas), Texaphor ^® 963, 3241 and 3250 (polymers, Henkel), Rilanit ^® types (Henkel), thixcin ^® E and R (castor oil derivatives, Rheox), Thixatrol ^® ST and GST (castor oil derivatives, Rheox), Thixatrol ^® SR, SR 100, TSR and TSR 100 (polyamide polymers, Rheox), Thixatrol ^® 289 (polyester Polymer, Rheox) as well as the different MPA ^® types X, 60-X, 1078-X, 2000-X and 60-MS (organic compounds, Rheox).

The auxiliaries mentioned can be used in the detergent components according to the invention in varying amounts, depending on the material and active substance used. Usual use concentrations for the abovementioned anti-settling, anti-floating, thioxotropic and dispersing agents are in the range from 0.5 to 8.0% by weight, preferably between 1.0 and 5.0% by weight, and particularly preferably between 1.5 and 3.0 wt .-%, each based on the total amount of meltable substance and active substances.

Particularly preferred emulsifiers in the context of the present invention are polyglycerol esters, in particular esters of fatty acids with polyglycerols. These preferred polyglycerol esters can be described by the general formula V.

R ¹

HO- [CH CH-CH ₂ -O] _n -H (V), m the R ¹ in each Glyceπneinheit independently of one another is H or a fatty acyl radical having 8 to 22 carbon atoms, preferably having 12 to 18 carbon atoms, and n is a number between 2 and 15, preferably between 3 and 10.

These polyglycine nests are known in particular with the degrees of polymerization n = 2, 3, 4, 6 and 10 and are commercially available. Since substances of the type mentioned are also widely used in cosmetic formulations, a number of these substances are also classified in the INCI nomenclature (CTFA International Cosmetic Ingredient Dictionan 'and Handbook, 5' Edition, The Cosmetic, To etry and Fragrance Association, Washington, 1997 ). This standard cosmetic work contains, for example, information on the keywords POLYGLYCERYL-3-BEESWAX, POLYGLYCERYL-3-CETYL ETHER, POLYGLYCERYL-4-COCOATE, POLYGLYCERYL-10-DECALINOLEATE, POLY- GLYCERYL-10-DECAOLETELARY POLYGLYTE GLYCERYL-2-DIISOSTEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLY- GLYCERYL-10-DIISOSTEARATE, POLYGLYCERYL-2-DIOLEATE, POLY- GLYCERYL-3-DIOLEATE, POLYGLYCERYL-6-DIOLYATELY POLYGLY DISTEARATE, POLYGLYCERYL-6-

DISTE ARATE, POLYGLYCERYL-10-DISTEARATE, POLYGLYCERYL- 10- HEPT AOLE ATE, POLY-GYLCERYL- 12-H YDROXYSTE ARATE,

POL YGL YCERYL- 10-HEPT ASTE ARATE, POL YGL YCERYL-6-HEXAOLE ATE, POLYGLYCERYL-2-ISOSTEARATE, POLY-GLYCERYL-4-ISOSTEARATE, POLY- GLYCERYL-6-ISOSTEARATE, POLY-GL YCERYL, 10 POLY

LYCERYLMETH ACRYL ATE, POLYGL YCERYL- 10-M YRISTATE,

POLYGLYCERYL-2-OLEATE, POLYGL YCERYL-3-OLEATE, POLYGL YCERYL-4- OLEATE, POLYGLYCERYL-6-OLEATE, POLYGLYCERYL-8-OLEATE,

POLYGLYCERYL- 10-OLE ATE, POL YGL YCERYL-6-PENT AOLE ATE,

POL YGL YCERYL- 10-PENTAOLE ATE, POLYGLYCERYL-6-PENTASTEARATE, POLYGLYCERYL- 10-PENTASTEARATE, POLYGL YCERYL-2-SESQUI-

IOSOSTEARATE. POLYGL YCERYL-2-SESQUIOLEATE, POLYGLYCERYL-2-STEARATE, POLYGLYCERYL-3-STEARATE, POLYGLYCERYL-4-STEARATE, POLYGL YCERYL-8-STEARATE, POLYGLYCERYL- 10-STEARATE, POLYGL YETERYIS-2-STEELATE TETRAOLEATE, POLYGLYCERYL-2-TETRASTEARATE, POLYGL YCERYL-2-TRIISOSTEARATE, POLYGLYCERYL-10-TRIOLE ATE, POLYGLYCERYL-6-TRISTEARATE. The commercially available products from different manufacturers, which are classified under the abovementioned keywords in the work mentioned, can advantageously be used as emulsifiers in process step b) according to the invention.

Another group of emulsifiers which can be used in the rinse aid particles according to the invention are substituted silicones which carry side chains reacted with ethylene or propylene oxide. Such polyoxyalkylene siloxanes can be described by the general formula VI

R 'R ¹ R ¹

H ₃ C-Si-O- [Si-O] _n -Si-CH ₃ (VI),

R 'R ¹ R'

in which each radical R ¹ independently of one another for -CH or a polyoxyethylene or propylene group - [CH (R ² ) -CH ₂ -O] _x H group, R ² for -H or -CH ₃ , x for a Number between 1 and 100, preferably between 2 and 20 and in particular less than 10, and n indicates the degree of polymerization of the silicone.

Optionally, the polyoxyalkylenesiloxanes mentioned can also be etherified or esterified on the free OH groups of the polyoxyethylene or polyoxypropylene side chains. The unetherified and unesterified polymer made from dimethylsiloxane with polyoxyethylene and / or polyoxypropylene is referred to in the INCI nomenclature as DIMETHICONE COPOLYOL and is known under the trade names Abil * B (Goldschmidt), Alkasil ^® (Rhόne-Poulenc), Silwet ^® (Union Carbide) or Belsil ^® DMC 6031 commercially available.

DIMETHICONE COPOLYOL ACETATE esterified with acetic acid (for example Belsil ^® DMC 6032, -33 and -35, Wacker) and DIMETHICONE COPOLYOL BUTYL ETHERS (e.g. KF352A, Shin Etsu) can also be used as emulsifiers in the context of the present invention.

As with the fusible substances and the other ingredients, the emulsifiers also apply to a wide range of uses. Usually emulsifiers of the type mentioned make up 1 to 25% by weight, preferably 2 to 20% by weight and in particular 5 to 10% by weight of the weight of the detergent component.

As already mentioned above, the physical and chemical properties of the detergent components according to the invention can be varied in a targeted manner by a suitable choice of the ingredients a) to d). If, for example, only ingredients are used that are liquid at the melting temperature of the mixture, it is easy to produce single-phase mixtures which are characterized by special storage stability even in the molten state. The addition of solids, such as color pigments or substances with higher melting points, automatically leads to two-phase mixtures, which, however, also have excellent storage stability and an extremely low tendency to separate.

Regardless of the composition of the detergent components according to the invention, those detergent components are preferred which are characterized by a melting point between 50 and 80 ° C, preferably between 52.5 and 75 ° C and in particular between 55 and 65 ° C.

At room temperature, the detergent components according to the invention are solidified mixtures of the ingredients mentioned, which can take on any external shape. It is also possible to apply the mixtures as a melt to carriers and thus to provide carrier material-based cleaning agent components which, at room temperature, consist of carrier material (s) and a melt solidified on these carrier materials. Suitable carrier materials are all solids which do not soften at the temperature of the melt and which are also sufficient have large absorption capacity for the melt. Particularly preferred carrier materials are builders, which are described in detail below.

Another object of the present invention is a process for the production of particulate detergent components, which is characterized in that a melt of a) 10 to 90 wt .-% surfactant (s), b) 10 to 90 wt .-% fatty substances), c) 0 to 70% by weight of meltable substance (s) with a melting point above 30 ° C. and d) 0 to 15% by weight of further active ingredients or auxiliary substances are applied to one or more carrier materials and the mixture is shaped.

In this variant of the method, a melt is first produced which can contain further active ingredients and auxiliaries. This is placed on a carrier material and processed to give a shape in a mixture with this carrier material.

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

The melt can be applied to the carrier material in all customary mixing devices. The shaping processing step for the mixture of melt and carrier material is likewise not subject to any procedural restrictions, so that the person skilled in the art can also select from the processes familiar to him. In tests by the applicant, methods have been found to be preferred in which the shaping processing is carried out by granulating, compacting, pelleting, extruding or tableting. The process according to the invention comprises the application of melts from the ingredients a) to d) to carrier materials. In principle, the melt and carrier (s) can be present in varying amounts in the resulting rinse aid particles. Preferred processes are characterized in that a mixture of 5 to 50% by weight, preferably 10 to 45% by weight, particularly preferably 15 to 40% by weight and in particular 20 to 35% by weight of a melt of the ingredients a) to d) and 50 to 95% by weight, preferably 55 to 90% by weight, particularly preferably 60 to 85% by weight and in particular 65 to 80% by weight of carrier material (s) is shaped.

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

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

Another object of the present invention is therefore, in a first embodiment, a process for producing prilled detergent components, in which a melt is made from a) 10 to 90% by weight of surfactant (s), b) 10 to 90% by weight of fatty substances) , c) 0 to 70% by weight of meltable substance (s) with a melting point above 30 ° C. and d) 0 to 15% by weight of further active substances and / or auxiliary substances are injected into a cold gas stream.

The method according to the invention, which is briefly referred to as prilling, comprises the production of granular bodies from meltable substances, the melt being obtained from the contents. substances a) to d) is sprayed at the top of a tower m of defined droplet size, solidifies in free fall and the pellets 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 being below the melting temperature of the melt. To avoid long drops, cooled gases are often used, for example with frozen air or even liquid nitrogen, which is sprayed into the spray towers

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

An alternative method of filling is pastil production. A further embodiment of the present invention therefore provides a process for producing pastile-containing detergent components, in which a melt is made from a) 10 to 90% by weight of surfactant (s), b) 10 to 90% by weight of fatty substances), c ) 0 to 70% by weight of meltable substance (s) with a melting point above 30 ° C. and d) 0 to 15% by weight of further active ingredients and / or auxiliaries, metered onto cooled pastil plates

The pastilheren comprises the metering of the melt from the respective ingredients onto a (cooled) belt or rotating, inclined plates, which have a temperature below the melting temperature of the melt and are preferably cooled below room temperature. Here, too, process variants can be carried out in which the pastil maker plates are deep-frozen are. However, measures must be taken to prevent the condensation of air humidity

Pastil production produces larger particles which have sizes between 2 and 10 mm, preferably between 3 and 6 mm, in the technically customary processes The use of cooling rollers is an even more cost-effective variant for producing particulate cleaning agent components of the composition mentioned from melts. Another object of the present invention is therefore a process for the production of particulate detergent components, in which a melt of a) 10 to 90 wt .-% surfactant (s), b) 10 to 90 wt .-% fat), c) 0 up to 70% by weight of meltable substance (s) with a melting point above 30 ° C. and d) applying or spraying 0 to 15% by weight of further active substances and / or auxiliary substances onto a chill roll, scraping off the solidified melt and, if necessary crushed.

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

Of course, it is also possible according to the invention to compress the particulate compositions into a shaped body or an area thereof. This molded body can then be metered by the consumer, for example, but it can also be added in powder form. It is also possible to use the particulate compositions, in particular the prills, pastilles or products from the chill roll, as a tablettable premix and to use them in the production of multiphase moldings. Here, the compression then provides, for example, multi-layer tablets, one layer of which has the composition of a conventional detergent tablet, the other layer has the composition of the detergent component according to the invention, which also unfolds its advantage in this form of supply.

Multi-phase moldings can also be produced by producing moldings with cavities, for example troughs or through holes, and these cavities. can then be filled with other moldings. In the present case, it has proven useful that the “basic molded body”, ie the tablet which has a cavity, has the composition of a detergent tablet, while the molded body contained in the cavity is a molded body which has been pressed from prills, pastilles or flakes Adhesion of the two molded bodies to one another can be achieved by gluing the two molded bodies together, but it is also possible to press the molded bodies onto or into one another, and also into one another, in which the adhesion is achieved by the geometrical design of the cavity and filling , is possible.

As a manufacturing method, for example, the production of the molded body by separate production (molding) of a basic molded body a) and a core molded body b), which is preferably pressed from prills of the cleaning agent components according to the invention, the joining and the final application of both parts is preferred.

The production of molded articles from particulate detergent components according to the invention can be carried out using standard tabletting processes. These are described in detail below.

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the form of presentation from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.

The shaped body produced can assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, do-decahedral, octahedral, conical, pyramidal, five, ellipsoid -, hexagonal and octagonal prismatic and rhombohedral shapes are preferred. Completely irregular too Base areas such as arrow or animal shapes, trees, clouds, etc. can be realized. If the molded body has corners and edges, these are preferably rounded. As an additional optical differentiation, an embodiment with rounded corners and beveled (“chamfered”) edges is preferred.

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

The present invention therefore furthermore relates to the use of particulate detergent components composed of a) 10 to 90% by weight of surfactant (s), b) 10 to 90% by weight of fatty substances), c) 0 to 70% by weight of meltable Substance (s) with a melting point above 30 ° C. and d) 0 to 15% by weight of further active ingredients and / or auxiliaries in cleaning agents for automatic dishwashing.

These machine dishwashing detergents (MGSM) can be liquid or solid, the solid form of supply being of far greater importance. Solid machine dishwashing detergents can be given to the consumer as a "powder" or as a tablet, and the detergent components of the present invention can be incorporated into both forms.

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) 10 to 90 wt .-% surfactant (s), b) 10 to 90 wt .-% fat), c) 0 to 70 wt .-% meltable substance (s) with a melting point above 30 ° C and d ) 0 to 15 wt .-% contain other active ingredients and / or excipients.

The ingredients of automatic dishwashing detergents are described below. Some of these can also be contained as ingredient d) or carrier materials in the detergent components according to the invention.

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

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _2x + ι 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 Si2θ ^' yH2θ 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 module Na2θ: Siθ2 of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which dissolve are hesitant and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compaction or by overdrying. In the context of this invention, the term "amoφh" is also understood to mean "roentgenamoφh". 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 integrated in such a way 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 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 compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried x-ray silicates.

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

nNa ₂ O ^• (ln) K ₂ O ^• Al ₂ O ₃ ^' (2 - 2.5) SiO ₂ ^' (3.5 - 5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

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

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ θ ₇ ) at 200 ° C, and at higher temperatures in sodium trimetaphosphate (Na ₃ P ₃ θ9 and Maddrell's salt (see below) pass over. NaH ₂ PO reacts acidic; it forms when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, Potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 ^'3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO) _x ] and is readily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na2HPO, is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gladly ^'3 , water loss at 95 °), 7 mol. (Density 1.68 gladly ^"3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water (density 1.52 gladly ^{" 3} , melting point 35 ° with the loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes into the diphosphate Na P ₂ O ₇ when heated to a greater extent. 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, is an amorphous, white salt that is easily soluble in water.

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

Tetrasodium diphosphate (sodium pyrophosphate), Na P ₂ O ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), KP 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, wherein the pH value of l% solution at 25 ° 10.4. Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P Oιo (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na that crystallizes with 6 H ₂ O. with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ Oιo (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P ₂ θ ₅ , 25% K ₂ O) on the market. 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 trimethosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH -> Na K ₂ P ₃ O, ₀ + H ₂ O

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and Potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

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

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

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

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

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which are generally determined 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. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

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

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

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

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

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers , Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing effect.

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 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 can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring for the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminisisuccinate, are further suitable cobuilders. Ethylenediamine-N, N ^'- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts for use in zeolite-containing and / or silicate-containing formulations are 3 to 15% by weight.

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

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

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders. Preferred particulate machine dishwashing detergents according to the invention contain builders in amounts of from 20 to 80% by weight, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the weight of the agent.

In addition to the builders, substances from the groups of surfactants, bleaching agents, bleach activators, enzymes, polymers and dyes and fragrances are particularly important ingredients of cleaning agents. Important representatives from the substance classes mentioned are described below, reference being made to the explanations above regarding the description of the surfactants.

Preferred particulate machine dishwashing detergents further contain one or more substances from the groups of bleaching agents, bleach activators, bleaching catalysts, surfactants, corrosion inhibitors, polymers, dyes and fragrances, pH regulators, complexing agents and the enzymes.

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H2O2 in water. Further bleaching agents that can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H2O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodeconetic acid.

"Sodium percarbonate" is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na2CO -3 HO ₂ and is therefore not peroxy carbonate. Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 ^"3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by ethanol precipitation from a solution of sodium carbonate in hydrogen peroxide, but was erroneously viewed carbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, but 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 in fluidized bed dryers at 90.degree. The bulk density of the finished product can vary between 800 and 1200 g / 1 depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, according to the invention, all types of percarbonate that are commercially available, such as those offered by the companies Solvay Interox, Degussa, Kemira or Akzo, can be used.

Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monophosphate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxythoxy acid oxo-phthalimidoxythoxy acid oxaloacetic acid [ε-phthalimidoxythalo acid] (PAP)], o-carboxybenzamido 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, diperocysoxybracic acid, diper acrylic acid, the diperoxy-phthalic acids, 2-decyldiperoxybutane-l, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

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

The bleaches mentioned can also be introduced into the automatic dishwashing detergents according to the invention to achieve “post-bleaching”, in part via the detergent components according to the invention, where they constitute ingredient d).

Bleach activators which 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 anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine DADHT and isatoic anhydride ISA. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), car- bonic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-Moφholinium-Acetonitril-Methylsulfat (MMA), and those from the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconol / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used.

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

Bleach activators from the group of multiply acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (N-) or iso-NOBs iso , n-Methyl-Moφholinium-Acetonitril-Methylsulfat (MMA), preferably in amounts up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferred 2 to 6 wt .-% based on the total agent used.

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

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

Dyes and fragrances can be added to the automatic dishwashing detergents according to the invention in order to improve the aesthetic impression of the resulting products and, in addition to the performance, give the consumer a visually and sensorially "typical and non individual "fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Perfume oils of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p - tert-Butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, for example, the jonones, α-isomethylionone and methylcedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, hydrocarbons include phenylethylol alcohol and the phenylethyl alcohol, and head mainly the typhons such as lemons and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning agents according to the invention, but it can also be advantageous to apply the fragrances to carriers. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries. Incorporation of the fragrances as ingredient d) into the detergent components according to the invention is also possible and leads to a scent impression when the machine is opened.

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

The cleaning agents according to the invention can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being of particular importance in the field of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) 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 particulate machine dishwashing detergents according to the invention can contain the detergent components according to the invention in varying amounts, the content being higher or lower depending on the composition of the detergent components and depending on the desired application success. Preferred particulate machine dishwashing detergents contain 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, in each case based on the total agent. The composition of the detergent components according to the invention can be designed such that they do not dissolve in the main rinse cycle (and also in optional pre-rinse cycles) or only to a minor extent. This ensures that the surfactants are only released in the final rinse cycle and develop their effect here. In addition to this chemical assembly, depending on the type of dishwasher, physical assembly is required so that the rinse aid items are not pumped out when the water is changed in the machine and are therefore no longer available for the rinse aid. Standard household dishwashers contain a sieve insert in front of the drain pump, which pumps the water or cleaning solution out of the machine after the individual cleaning cycles, which is intended to prevent the pump from becoming blocked by dirt residues. If heavily soiled crockery is washed by the consumer, this sieve insert must be cleaned regularly, which is easily possible due to the easy accessibility and removability. The size and shape of the detergent components according to the invention are now preferably designed such that they do not pass the sieve insert of the dishwasher even after the cleaning cycle, ie after exposure to movement in the machine and the cleaning solution. This ensures that there are detergent components in the dishwasher in the rinse cycle, which release the active substance (s) under the action of the warmer water and bring the desired rinse aid effect. Particulate machine dishwashing detergents preferred in the context of the present invention are 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 20 mm.

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

If the cleaning agents according to the invention are formulated as a powder mixture, partial segregation can occur on the one hand when the package is shaken, in particular when the sizes of the cleaning agent component and cleaning agent matrix are very different, on the other hand the dosage can be different in two successive cleaning cycles, since the consumer is not always mandatory dosed the same amount of detergent and detergent component. If it is desired to technically always use the same amount per cleaning cycle, this can be achieved by packaging the agents according to the invention in bags made of water-soluble film, which is familiar to the person skilled in the art. The present invention also relates to a particulate machine dishwashing agent which is characterized in that a metering unit is welded into a bag made of water-soluble film.

As a result, the consumer only has to insert a bag, which contains, for example, a detergent powder and a plurality of optically prominent detergent component particles, into the dispenser compartment of his dishwasher. This embodiment of the present invention is therefore an optically attractive alternative to conventional detergent tablets.

Since the consumer not only uses particulate cleaning agents for machine dishwashing, but also wants to use moldings, these are a further subject of the present invention. For this purpose, the melt can be formulated from the ingredients a) to d) as a phase of a shaped body, which has, for example, the shape of a layer, a core-shaped insert, etc. Another object of the present invention is thus a multi-phase detergent molded article for machine dishwashing, containing builders and optionally further detergent ingredients, in which at least one phase consists of a) 10 to 90% by weight of surfactant (s), b) 10 up to 90% by weight of fatty substances), c) 0 to 70% by weight of meltable substance (s) with a melting point above 30 ° C. and d) 0 to 15% by weight of further active ingredients and / or auxiliaries.

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

The shaped bodies according to the invention can take on any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, five, ellipsoidal -, Hexagonal and octagonal-prismatic and rhombohedral shapes are preferred. Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the shaped bodies according to the invention have corners and edges, they are preferably rounded. As an additional optical differentiation, an embodiment with rounded corners and beveled (“chamfered”) edges is preferred. Instead of the layer structure, molded bodies can also be produced which contain the cleaning agent component according to the invention in the form of other phases. It has proven useful here to produce basic molded articles which have one or more cavities and to fill the melt from the constituents a) to d) of the detergent component according to the invention into the cavity and to solidify it there. This manufacturing process results in preferred multi-phase detergent tablets which consist of a basic molded article which has a cavity and an at least partially contained in the cavity.

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

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

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

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

In the case described above, the part at least partially contained in the cavity consists solely of the ingredients a) to d) of the detergent components. It however, it is also possible to incorporate 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 consists of a) 10 to 90% by weight of surfactant (s), b) 10 to 90% by weight of fatty substances), c) 0 to 70 % By weight of meltable substance (s) with a melting point above 30 ° C. and d) 0 to 15% by weight of further active substances and / or auxiliaries.

The size of the trough or the through hole in comparison to the entire molded body depends on the intended use of the molded body. The size of the cavity can vary depending on how much more active substance the remaining hollow volume is to be filled with and whether a smaller or larger amount of detergent component is to be contained. Regardless of the intended use, detergent tablets are preferred in which the volume ratio of the pressed part (“basic tablet”) to the detergent component is 2: 1 to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1.

In addition to the volume ratio mentioned, a mass ratio of the two parts can also be specified, the two values correlating with one another via the densities of the basic molded body or the detergent component. Irrespective of the density of the individual parts, detergent tablets according to the invention are preferred, in which the weight ratio of base tablets to detergent components is 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and is in particular 4: 1 to 30: 1.

Analogous information can also be given for the surfaces that are visible from the basic molded body or from the detergent component. Here, detergent or detergent tablets are preferred, in which the outwardly visible surface of the detergent component is 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 basic molded body are preferably optically distinguishable. In addition to the optical differentiation, application-technical advantages can be achieved by different solubilities of the different molded body areas. Detergent and cleanser molded bodies, in which the detergent component dissolves faster than the basic molded body, are preferred according to the invention by Incorporation of certain components can on the one hand accelerate the detachment of the detergent component in a targeted manner, on the other hand the release of certain ingredients from the detergent component can lead to advantages in the washing or cleaning process

Of course, detergent or cleaning agent bodies according to the invention are also preferred, in which the detergent component dissolves later in the washing program than the basic molding body. Performance advantages from this delayed release can be achieved, for example, by using a slow-release detergent component to release active substance (s) only in later rinse cycles. For example, in machine dishwashing, slower-soluble detergent components can be used to achieve that further active substance in the rinse cycle (s) is / are available. Additional substances such as non-ionic surfactants, acidifying agents, soil-release polymers, etc. can be used to improve the rinse aid results. Perfume is also incohered without any problems "are removed when the machine is opened. The ingredients acidifying agents, soil-release polymers, etc. are based on the cleaning agent components according to the invention, then ingredients d)

The Basisformkoφer has a high specific weight in preferred embodiments of the present invention. Detergent and shaped body, which are characterized in that the basic shaped body has a density above 1000 gdm ^{" 3} , preferably above 1025 gdm ^"3 , particularly preferably above 1050 gdm" 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 incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times. Tablet disintegrants or disintegration accelerators are used according to Rompp (9th edition, Vol. 6, S 4440) and Voigt " Textbook of pharmaceutical technology "(6th edition, 1987, S 182-184) understood auxiliary substances which ensure the rapid disintegration of tablets in water or gastric juice and the release of the pharmaceuticals in an absorbable form

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

Preferred cleaning agent moldings contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, in each case based on the weight of the molding body. Contains only the basic molding disintegration aid, so the information given relates only on the weight of the basic shaped body. When incinerating disintegration aids into the detergent components according to the invention, those pay as ingredient d)

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent molds contain such a disintegrant based on cellulose in quantities of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight. contain rice ne cellulose has the formal gross composition (C ₆ Hιoθ ₅ ) _n and, formally speaking, represents a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 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 hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

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

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

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

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

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and bicarbonates may be preferred for reasons of washing technology.

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

Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

In the context of the present invention, preference is given to shaped detergent bodies in which a substance from the group of the organic di-, tri- and oligocarboxylic acids or mixtures of these are used as acidifying agents in the effervescent system. The particulate detergents and / or detergent tablets can - like the detergent components according to the invention - be packaged after manufacture, the use of certain packing systems having proven particularly useful. A further aspect of the present invention is a combination of (a) particulate cleaning agent (s) according to the invention and / or (a) washing or cleaning agent shaped body (s) according to the invention and a cleaning agent and / or the washing and cleaning agent shaped body (s) containing packaging system, the packaging system having a moisture vapor transmission rate of 0.1 g / m '/ 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 cleaning agent and / or detergent and cleaning agent body (s) and packaging system according to the invention has a moisture vapor permeability rate of 0.1 g / m ² / day to less than 20 g / m ² / day, if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. The specified temperature and humidity conditions are the test conditions that are mentioned in 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 by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring water vapor transmission of materials in sheet form") and in the TAPPI standard T464 m -45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being 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 sealed with the material to be tested (permeation surface), the weight increase in calcium chloride and the exposure time __ _n _ 2244 1100000000 xx \, FDDR = [g I m- 124h

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

The relative equilibrium humidity, often referred to as “relative air humidity”, is 85% at 23 ° C. when measuring the moisture vapor permeability rate in the context of the present invention. The capacity of air for water vapor increases with temperature up to a respective maximum content, the so-called saturation content , and is given in g / m ^3. For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor, at a temperature of 11 ° saturation already exists with 10 g of water vapor, which is the relative humidity expressed as a percentage 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 one cools this air, then the saturation (100% r.L.) is reached at the so-called dew point (in the example: 14 °), ie at further When cooling, a precipitate is formed in the form of fog (dew). Hygrometers and psychrometers are used for the quantitative determination of moisture.

The relative equilibrium humidity of 85% at 23 ° C can, for example, be adjusted to +/- 2% RH in the laboratory with moisture control depending on the device type. Precise adjustment Even with saturated solutions of certain salts, constant and well-defined relative atmospheric humidities form in closed systems at a given temperature, which are based on the phase equilibrium between the partial pressure of the water, saturated solution and the soil body.

The combinations according to the invention can of course in turn be packaged in secondary packaging, for example cardboard boxes or trays, with no further requirements having to be made of the secondary packaging. Secondary packaging is therefore possible, but not necessary. Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m / day to less than 15 g / m7 day

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

The packaging system of the combination according to the invention can consist of a wide variety of materials and can take on any external shape. However, for economic reasons and for reasons of easier processing, packaging systems are preferred in which the packaging material is light in weight, easy to process and inexpensive. In combinations preferred according to the invention, the packaging system consists of a sack or pouch made of single-layer or laminated paper and / or plastic film. The detergent tablets can be unsorted, that is, as a loose fill, filled into a bag made of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferred to fill the detergent and cleaning product tablets individually or in groups in sacks or bags. For individual application units of the detergent tablets that are in a sack or bag, the term "flow pack" has become common in technology. Such "flow packs" can then - again preferably sorted - be optionally packed in repackaging, which the compact offer form of the molded body underlines.

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

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

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

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

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

Also preferred are embodiments of the combination according to the invention in which the packaging system is designed to be resealable. Combinations in which the packaging system has a microperforation can also be preferably implemented according to the invention. As mentioned above, detergent components, detergent compositions or detergent tablets for automatic dishwashing can be produced by the methods according to the invention. Accordingly, a cleaning method for cleaning dishes in a dishwasher is characterized in that one or more particulate detergents according to the invention and / or one or more detergent tablets according to the invention insert and insert the dosing chamber of the dishwasher Rinsing program can run, in the course of which the metering chamber opens and the cleaning agent (s) and / or the molded body (s) are dissolved, another object of the present invention.

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

Examples:

By mixing the particulate ingredients b) (fat) and c) (meltable substance) dry, melting and adding ingredient a) (surfactant) and optionally adding other ingredients d) melts were produced, the composition of which is given in the table below.

Table 1: Melting [% by weight]

Poly Tergent SLF-18B-45: alcohol alkoxylate from Olin Chemicals, softening point 25-45 ° C. Compositions 1 to 15 according to the invention could be grooved without problems. pastill or shape into particles with chill rolls. The prills had particle sizes between 800 and 1200 μm, the pastilles had sizes between 3 and 6 mm and the particles from the chill roll treatment had an average particle size of 800 μm.

In addition, detergent tablets for machine dishwashing were produced, which were filled with melts of the compositions 1 to 15 according to the invention.

For this purpose, two-layer rectangular shaped bodies were produced by pressing two different premixes, which had a hollow in the form of a semi-ellipse. The molded bodies consisted of 75% by weight of the lower phase and 25% by weight of the upper phase. The following table shows the composition (in% by weight, based on the respective premix) of the two premixes and thus of the two different phases of the mold body:

Compositions 1 to 15 according to the invention were melted and poured into the trough shaped body in a weight ratio of 96 to 4 (data in% by weight, based on the completely filled shaped body): the filled shaped body was allowed to cool at room temperature and subsequently individually packed.

The filled trough shaped bodies have significantly better rinse aid performance compared to shaped bodies composed analogously, in which the ingredients of compositions 1 to 15 according to the invention were added individually to premix 1 and pressed together with this.

All of the above-mentioned tests were carried out in several commercially available dishwashers by several test persons, the moldings being placed in the metering chamber of the machine and a 55 ° C. program being carried out with the machine loaded. No detergent or rinse aid was used in any of the tests.

The moldings fillings do not dissolve in conventional 50/55 ° C main wash. After the hot rinse cycle, there are no residues of compositions 1 to 15 in the dishwasher, i.e. the fillings of the molded articles dissolve without residue in the rinse cycle.

Claims

claims:

1. Detergent component containing a) 10 to 90% by weight of surfactant (s), b) 10 to 90% by weight of fatty substances), c) 0 to 70% by weight of meltable substance (s) with a melting point above 30 ° C and d) 0 to 15 wt .-% of other active ingredients and / or auxiliaries.

2. Detergent component according to claim 1, characterized in that it contains as ingredient a) 15 to 80, preferably 20 to 70, particularly preferably 25 to 60 and in particular 30 to 50 wt .-% surfactant (s).

3. Detergent component according to one of claims 1 or 2, characterized in that it contains as ingredient b) 12.5 to 85, preferably 15 to 80, particularly preferably 17.5 to 75 and in particular 20 to 70% by weight of fatty substances) ,

4. Detergent component according to one of claims 1 to 3, characterized in that it contains as ingredient c) 0 to 65, preferably 0 to 60, particularly preferably 0 to 55 and in particular 0 to 50 wt .-% meltable substance (s).

5. Detergent component according to one of claims 1 to 4, characterized in that it contains as the ingredient a) anionic (s) and / or nonionic (s) surfactant (s), preferably nonionic (s) surfactant (s).

6. Detergent component according to one of claims 1 to 5, characterized in that it contains as ingredient a) nonionic (s) 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 contains.

7. detergent component according to one of claims 1 to 6, characterized in that it contains as the ingredient a) ethoxylated (s) nonionic surfactant (s), the / which from C ₆ - ₂ o- Monohydroxyalkanols or C _ö - ₂₀ alkylphenols or Ci ₆ - 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

Detergent component according to one of claims 1 to 7, characterized in that it contains as ingredient a) ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight - Make up% of the total molecular weight of the non-ionic surfactant

Detergent component according to one of Claims 1 to 8, characterized in that it contains, as 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 represents a value of at least 15.

Detergent component according to one of claims 1 to 9, characterized in that it contains, as ingredient a) end-capped poly (oxyalkyherten) nonionic surfactants of the formula

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

contains, 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 is} H or a methyl, ethyl. n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j for values between 1 and 12. preferably between 1 and 5 are, with surfactants of the type R ¹⁰ O [CH ₂ CH (R ³ ) O] _x CH _: 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.

11. Detergent component according to one of claims 1 to 10, characterized in that it contains as ingredient b) one or more substances from the groups of fatty alcohols, fatty acids and fatty acid esters.

12. Cleaning agent component according to one of claims 1 to 11, characterized in that it comprises as ingredient b) one or more Cι _0-3 o-fatty alcohols, preferably C _2-24 fatty alcohols, with particular preference from 1-hexadecanol, 1-octadecanol, 9-cis-octadecen-l-ol, all-cis-9,12-octadecadien-l-ol, all-cis-9,12,15-octadecatrien-1-ol, 1-docosanol and mixtures thereof.

13. Detergent component according to one of claims 1 to 12, characterized in that it contains as ingredient c) one or more substances with a melting range between 30 and 100 ° C, preferably between 40 and 80 ° C and in particular between 50 and 75 ° C, contains.

14. Detergent component according to one of claims 1 to 13, characterized in that it contains as ingredient c) at least one paraffin wax with a melting range of 30 ° C to 65 ° C.

15. Detergent component according to one of claims 1 to 14, characterized in that it contains as ingredient c) at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG).

16. Detergent component according to one of claims 1 to 15, characterized in that it contains as ingredient d) further active ingredients and / or auxiliary substances from the groups of dyes. Fragrances, anti-settling agents, floating agents, anti-floating agents, thixotropic agents and dispersing agents in amounts of 0 to 10% by weight, preferably from 0.25 to 7.5% by weight, particularly preferably from 0.5 to 5% by weight and in particular from 0.75 to 2.5% by weight.

17. Detergent component according to one of claims 1 to 16, characterized by a melting point between 50 and 80 ° C, preferably between 52.5 and 75 ° C and in particular between 55 and 65 ° C.

18. A process for the production of particulate detergent components, characterized in that a melt of a) 10 to 90 wt .-% surfactant (s), b) 10 to 90 wt .-% fat), c) 0 to 70 wt .-% % meltable substance (s) with a melting point above 30 ° C. and d) applying 0 to 15% by weight of further active substances and / or auxiliaries to one or more carrier materials and the mixture being shaped.

19. The method according to claim 18, characterized in that the shaping processing is carried out by granulating, compacting, pelleting, extruding or tableting.

20. A process for the production of veφrillter cleaning agent components, characterized in that a melt of a) 10 to 90 wt .-% surfactant (s), b) 10 to 90 wt .-% fat), c) 0 to 70 wt .-% % meltable substance (s) with a melting point above 30 ° C. and d) injecting 0 to 15% by weight of further active substances and / or auxiliaries into a cold gas stream.

21. A process for the production of pelletized detergent components, characterized in that a melt is formed a) 10 to 90 wt .-% surfactant (s), b) 10 to 90 wt .-% fat), c) 0 to 70 wt .-% meltable substance (s) with a melting point above 30 ° C and d ) 0 to 15% by weight of further active ingredients and / or auxiliaries metered onto chilled pastilling plates.

22. A process for the production of particulate detergent components, characterized in that a melt of a) 10 to 90% by weight of surfactant (s), b) 10 to 90% by weight of fatty substances), c) 0 to 70% by weight % meltable substance (s) with a melting point above 30 ° C and d) 0 to 15% by weight of further active substances and / or auxiliaries are applied or sprayed onto a cooling roll, the solidified melt is scraped off and, if necessary, comminuted.

23. Use of particulate detergent components composed of a) 10 to 90% by weight of surfactant (s), b) 10 to 90% by weight of fatty substances), c) 0 to 70% by weight of meltable substance (s) with a melting point above 30 ° C. and d) 0 to 15% by weight of further active ingredients and / or auxiliaries in cleaning agents for automatic dishwashing.

24. Particulate machine dishwashing detergent, containing builders and optionally further detergent ingredients, characterized in that it contains particulate detergent components which, based on their weight, a) 10 to 90 wt .-% surfactant (s), b) 10 to 90 wt .-% fat), c) 0 to 70 wt .-% meltable substance (s) with a melting point above 30 ° C and d) contain 0 to 15% by weight of further active ingredients and / or auxiliaries.

25. Particulate machine dishwashing detergent according to claim 24, characterized in that it contains builders in amounts of 20 to 80% by weight, preferably 25 to 75% by weight and in particular 30 to 70% by weight, in each case based on the Weight of the product.

26. Particulate dishwasher detergent according to one of claims 24 or

25, characterized in that it further contains one or more substances from the groups of bleaching agents, bleach activators, bleaching catalysts, surfactants, corrosion inhibitors, polymers, dyes and fragrances, pH adjusting agents, complexing agents and the enzymes.

27. Particulate dishwasher detergent according to one of claims 24 to

26, 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, in each case based on the total agent ,

28. Particulate dishwasher detergent according to one of claims 24 to

27, 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 20 mm.

29. Particulate dishwasher detergent according to one of claims 24 to

28, characterized in that it (without taking into account the particulate detergent component) has particle sizes between 100 and 3000 microns, preferably between 300 and 2500 microns and in particular between 400 and 2000 microns.

30. Particulate machine dishwashing detergent according to one of claims 24 to 29, characterized in that a metering unit is welded into a bag made of water-soluble film.

31. Multi-phase detergent molded article for machine dishwashing, containing builders and optionally further detergent ingredients, characterized in that at least one phase of a) 10 to 90 wt.% Surfactant (s), b) 10 to 90 wt.% Fatty substances ), c) 0 to 70% by weight of meltable substance (s) with a melting point above 30 ° C. and d) 0 to 15% by weight of further active substances and / or auxiliaries.

32. Mehφhasiger Reinigungsmittelformköφer according to claim 31, characterized in that the phases have the shape of layers and the molded body is 2-, 3- or 4-phase.

33. Mehφhasiger Reinigungsmittelformköφer according to claim 31, characterized in that it consists of a Basisformköφer, which has a cavity, and an at least partially contained in the cavity.

34. Mehφhasiger shaped detergent body according to claim 33, characterized in that the part contained in the cavity from a) 10 to 90 wt .-% surfactant (s), b) 10 to 90 wt .-% fat), c) 0 to 70 % By weight of meltable substance (s) with a melting point above 30 ° C. and d) 0 to 15% by weight of further active substances and / or auxiliaries.

35. Combination of (a) particulate cleaning agent (s) according to one of claims 24 to 30 and / or (a) washing or cleaning agent shaped body (s) according to one of claims 31 to 34 and one of the cleaning agent and / or the washing - Packaging system containing detergent and shaped articles, characterized in that the packaging system has a moisture vapor permeability rate of 0.1 g / m / day to less than 20 g / m / day if the packaging system is at 23 ° C and a relative equilibrium humidity of 85% is stored.

36. Cleaning method for cleaning dishes in a dishwasher, characterized in that one or more particulate detergent (s) according to any one of claims 24 to 30 and / or one or more detergent or cleaning agent shaped articles according to one of claims 31 to 34 in the The dosing chamber of the dishwasher is inserted and a rinsing program can be run, in the course of which the dosing chamber opens and the cleaning agent (s) and / or the molded body (s) are dissolved.

37. Cleaning method for cleaning dishes in a dishwasher, characterized in that one or more particulate cleaning agent (s) according to one of claims 24 to 30 and / or one or more detergent or cleaning agent shaped articles according to one of claims 31 to 34 with or without metering aid in the dishwasher's dishwasher and let a washing program run, in the course of which the cleaning agent (s) and / or the molded article (s) are dissolved.