DE19957505A1 - Detergent component with finely divided solids - Google Patents

Abstract

The invention relates to long-time stable mixtures (dispersions/emulsions) with only a slight tendency to separate, which provide effective and stable detergent components. Said mixtures contain 10 to 89.9 wt. % tenside(s), 10 to 89.9 wt. % meltable substance(s) with a melting point above 30 DEG C and a water solubility of less than 20 g/l at 20 DEG C, 0.1 to 15 wt. % of one or more solids, at least 90 wt. % of whose particles have a particle size of less than 300 mu m and optionally, 0 to 15 wt. % other active agents and/or auxiliary agents.

Description

The present invention is in the field of automatic dishwashing detergents household dishwashers. It concerns detergent components for the Use in machine dishwashing detergents (MGSM) and detergents together settlements and detergent tablets containing such components.

The mechanical cleaning of dishes in household dishwashers includes Usually a pre-wash, a main wash and a rinse cycle that by Intermediate rinse cycles are interrupted. On most machines, the pre-rinse cycle is for heavily soiled dishes can be switched on, but only in exceptional cases by the consumer chosen so that in most machines a main wash, an intermediate wash with pure Water and a rinse aid are performed. The main wash temperature varies depending on the machine type and program level selection between 40 and 65 ° C. In the rinse aid are added rinse aid from a dosing tank in the machine, usually as Main component contains non-ionic surfactants. Such rinse aids are in liquid form before and are widely described in the prior art. Your main task is Prevent limescale and deposits on the cleaned dishes. Besides water and weakly foaming nonionic surfactants often also contain hydrotopes, pH adjusters such as citric acid or scale-inhibiting polymers.

The storage tank in the dishwasher must be rinse-aid at regular intervals be filled, whereby one filling is sufficient for 10 to 50 rinse cycles, depending on the machine type. If you forget to fill the tank, glasses with limescale marks and  Unsightly toppings. In the prior art, there are therefore some proposed solutions, one Integrate rinse aid into the detergent for machine dishwashing.

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

The older German patent application DE 198 51 426.3 (Henkel KGaA) describes a method for the production of multi-phase detergent tablets, in which a particulate premix is pressed to form bodies which have a trough, the later with a separately produced melt from a meltable substance and an or several active substance (s) dispersed or suspended in it. The teaching too this document is bound to the "tablet" offer.

The melt suspensions or emulsions disclosed in the last-mentioned document point however, especially when incorporating surfactants as an active substance long-term stability in need of improvement. The meltable substances are said to Cooling the emulsion include the active ingredient and before premature release protect. if the emulsion is insufficiently stable, it separates in the molten state of the dosage in part, which leads to dosage accuracy. Slightly more stable Although emulsions can be dosed, they partially separate before solidification, so that the active substance is released early in the cleaning cycle. As a solution this document discloses the use of various aids or stabilizers. If solids However, no statements about their physical properties are mentioned made.

The present invention was based on the task of teaching the older German Patent application DE 198 51 426.3 to develop and long-term stable mixtures To provide, which do not tend to separate during the metering and cooling and so  deliver effective and stable detergent components. These long-term stable mixtures and the detergent components made from them should all known Advantages of the controlled release of ingredients, especially a rinse aid effect, usable for powder detergents as well as detergent tablets do.

It has now been found that separable-stable melts consist of meltable hydrophobic Substances with melting points above 30 ° C, surfactant (s) and optionally others Ingredients such as colors and fragrances, etc. can be produced if these mixtures contain at least 0.1% by weight of finely divided solid (s).

The melting point of such mixtures can be determined by the type and amount of each Ingredients, especially about the melting points and amounts of meltable Set substance (s) and surfactant (s) specifically to the desired value. Above the Separation-stable mixtures exist below the melting point, and solidify below the melting point Mixtures in any shape, which in the context of the present application as Detergent components are called.

The present invention relates to a detergent component which

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20 g / l at 20 ° C,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

contains, with the proviso that at least 90 wt .-% of the particles c) particle sizes below 300 microns exhibit.

The term "detergent component" in the context of the present Registration solidified melts from the ingredients a) to d), regardless of their Shaping. "Detergent components" in the sense of the present application are therefore for example scales, prills, lozenges, shaped body areas, shaped bodies themselves, etc. To the finest possible distribution of ingredient a) in a matrix of ingredient b) both ingredients are separated or melted together in a mixture,  optionally combined and stirred with the addition of c) and optional addition of d). The on this Melt suspension or emulsion prepared in this way, which is also briefly referred to below as "Mixture" is called, can then be converted into the desired shape.

Preferred detergent components contain as ingredient a) 15 to 80, preferably 20 to 70, particularly preferably 25 to 60 and in particular 30 to 50% by weight of surfactant (s). there can all surfactants from the groups of anionic, nonionic, cationic or amphoteric surfactants are used, preferred detergent components are characterized in that as ingredient a) anionic (s) and / or nonionic (s) Contain surfactant (s), preferably non-ionic surfactant (s).

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

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

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

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

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

Soaps are particularly suitable as further anionic surfactants. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearin acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and 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. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The given degrees of ethoxylation are 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 these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

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

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than that Half of it.

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

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

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

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

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

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

Particularly preferred are detergent components according to the invention, the one contain nonionic surfactant, which has a melting point above room temperature. Accordingly, preferred detergent components are characterized in that they are 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, the melting or softening points in the above Have low temperature, for example weakly foaming nonionic surfactants, which can be solid or highly viscous at room temperature. Become at Highly viscous nonionic surfactants used at room temperature, it is preferred that these have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas exhibit. Nonionic surfactants, which have a waxy consistency at room temperature, are also prefers.

Preferred nonionic surfactants to be used as solid at room temperature come from the groups of alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and mixtures 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 is nonionic surfactant with a melting point above room temperature an ethoxylated nonionic surfactant, which from the Reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

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

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

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated Monohydroxyalkanols or alkylphenols, which are also polyoxyethylene-polyoxypropylene Have block copolymer units. The alcohol or alkylphenol part of such Nonionic surfactant molecules preferably make up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such Nonionic surfactants. Preferred 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 up to 25 wt .-%, preferably up to 20 wt .-% and make up in particular up to 15% by weight of the total molar mass of the nonionic surfactant, contain.

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

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

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

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

in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon test 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, iso-propyl, n -Butyl, 2-butyl or 2-methyl-2-butyl, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≧ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

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

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

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

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x 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 carbon atoms, R ^{3 represents} H and x assumes values from 6 to 15.

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

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

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

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

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

The detergent components according to the invention contain one or as ingredient b) several fusible substances with a melting point above 30 ° C and are little to not water-soluble. These substances form the "matrix" in which the ingredient a) the detergent components according to the invention are present in finely divided form, these Distribution is stabilized by the special ingredient c). As part of the present  Detergent components preferred according to the invention contain 15 to 85 as ingredient b), preferably 20 to 80, particularly preferably 25 to 75 and in particular 30 to 70% by weight fusible substance (s).

By choosing the melting point of ingredient b), the temperature at which the detergent components according to the invention release the ingredients a) and optionally d), vary within wide limits. The remaining ingredients are below this temperature Protected from environmental influences.

To the meltable substances in the detergent components according to the invention are used, there are various requirements, on the one hand the melting or solidification behavior, but also the material properties of the Envelope in the solidified state, d. H. in the detergent components according to the invention affect. As the detergent component is permanently protected against transport or storage To be protected from environmental influences, the fusible substance must have a high stability against have, for example, shock loads occurring during packaging or transport. The Meltable substance should therefore either be at least partially elastic or at least plastic Have properties in order to avoid the occurrence of a shock load due to elastic or plastic To respond to deformation and not to break. The meltable substance should be an enamel range (solidification range) in such a temperature range in the other Ingredients of the detergent components according to the invention none too high thermal Exposed to stress. On the other hand, the melting range must be sufficiently high to provide effective protection for the at least slightly elevated temperature to offer included active substances. According to the invention, the meltable substances a melting point above 30 ° C, with detergent components are preferred that only fusible substances with melting points above 40 ° C, preferably above 45 ° C and especially above 50 ° C. Particularly preferred Detergent components contain one or more substances with one as ingredient b) 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 one Melting point shows how it usually occurs with pure, crystalline substances, but one possibly has a melting range spanning several degrees Celsius.

The fusible substance preferably has a melting range that is between approximately 52.5 ° C. and is about 80 ° C. In the present case, this means that the melting range within the specified temperature interval occurs 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. Under "Waxing" is understood to mean a number of natural or artificially derived substances that Usually melt above 50 ° C without decomposition and a little above the melting point are relatively low viscosity and non-stringy. They have a strong temperature dependent consistency and solubility.

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, Shellac wax, whale, lanolin (wool wax), or pretzel fat, mineral waxes such as Ceresin or Ozokerite (earth wax), or petrochemical waxes like petrolatum, paraffin waxes or Micro waxes.

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

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. Compounds made of are also usable as covering materials other classes of substances that meet the requirements regarding the softening point and the  Meet water solubility. Suitable synthetic compounds have, for example higher esters of phthalic acid, especially dicyclohexyl phthalate, which is commercially available under the Name Unimoll® 66 (Bayer AG) is available. Synthetic are also suitable waxes produced from lower carboxylic acids and fatty alcohols, for example dimyristyl Tartrate, which is available under the name Cosmacol® ETLP (Condea).

The shell preferably contained in the detergent components according to the invention substance a share of paraffin wax. That is, at least 10% by weight of the total contained meltable substances, preferably more, consist of paraffin wax. Especially paraffin wax contents (based on the total amount of meltable substance) of are suitable about 12.5% by weight, about 15% by weight or about 20% by weight, with even higher proportions of for example, more than 30% by weight may be particularly preferred. In a special one Embodiment of the invention consists of the total amount of meltable substance used made exclusively from paraffin wax.

Paraffin waxes show the other natural waxes mentioned within the scope of the present invention the advantage that in an alkaline detergent environment none Hydrolysis of the waxes takes place (as can be expected, for example, in the wax esters), because Paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially none Ingredients with a melting point of more than 70 ° C, particularly preferably of more than 60 ° C on. Shares of high-melting alkanes in the paraffin can fall below this Melting temperature in the detergent fleet undesirable wax residues on the cleaning surfaces or the goods to be cleaned. Such wax residues result usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided become.

Preferred detergent components contain at least one as ingredient b) Paraffin wax with a melting range from 30 ° C to 65 ° C.  

The content of the paraffin wax used is preferably at ambient temperature (in which Rule about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. Each The more solid wax components are present in a wax at room temperature, the more it is more useful in the context of the present invention. With increasing proportion of fixed Wax components increase the resilience of the detergent component to impact or rubbing against other surfaces, resulting in longer-lasting protection of the active ingredients leads. High levels of oils or liquid wax components can weaken the Particles lead, whereby pores are opened and the active ingredients to the above Be exposed to environmental influences.

In addition to paraffin, the meltable substance can also contain one or more of the waxes mentioned above or waxy substances. It should preferably be the fusible substance forming mixture should be such that the detergent component is at least largely are insoluble in water. The solubility in water should be about 10 mg / l at a temperature of about 30 ° C not exceed and are preferably below 5 mg / l.

In any case, however, the wrapping should preferably have the lowest possible water Solubility, even in water at elevated temperature, to have a temperature-independent Avoid release of the active substances as much as possible. Preferred Detergent components are therefore characterized in that the water solubility of ingredient b) at 20 ° C less than 15 g / l, preferably less than 10 g / l, especially is preferably less than 5 g / l and in particular less than 2 g / l. Is particularly preferred when the water solubility of ingredient b) is 20 ° C below the measurement limit, Substance b) is "water-insoluble" in the common sense.

The detergent components according to the invention contain 0.1 to 15% by weight as ingredient c). one or more solids, at least 90% by weight of the particles of c) Have particle sizes below 300 microns. Are in preferred detergent components the amounts of c) are within a narrow range, and also the particle sizes preferably even finer. So on the one hand detergent components are preferred that the Ingredient c) in amounts of 0.15 to 12.5, preferably 0.2 to 10, particularly preferably from 0.25 to 7.5 and in particular from 0.3 to 5 wt .-% contain, on the other hand  at least 90% by weight of the particles from c) in further preferred detergent components Particle sizes below 200 µm, preferably below 190 µm, particularly preferably below 175 µm, in particular below 150 µm and very particularly preferably below 100 µm.

It is particularly preferred if the ingredient c) has no particles at all that have a Have size over 200 microns, this particle size limit preferably even further is undercut. In particularly preferred detergent components Ingredient c) completely from particles with particle sizes below 200 microns, preferably below 175 µm, particularly preferably less than 150 µm and especially less than 100 µm.

All substances that are solid and that mentioned are suitable as ingredient c) Particle size criteria are sufficient. The term "solid" means that the ingredient c) remains solid even at the processing temperatures of ingredients a) to d) and not at the production of melts with melts or dissolved in other ingredients. Substances whose melting point is clear are preferably used as ingredient c) is above the melting point of the detergent component, for example at least 10 ° C above, preferably at least 25 ° C above and in particular at least 50 ° C above. It can also be preferred as infusible substances at conventional temperatures Use ingredient c).

In addition to inorganic salts, mineral substances such as silicates, silicas, aluinosilkates, organic solids, etc., especially the alkali metal salts of organic acids proven as ingredient c), the sodium and potassium salts being preferred. As organic Acids, the salts of which are preferred ingredients c), are suitable, for example, formic acid, Acetic acid, propionic acid, succinic acid, citric acid, fumaric acid, oxalic acid, malonic acid, Tartaric acid etc. are particularly preferred detergent components characterized in that they contain, as ingredient c), alkali metal salts of organic acids, preferably Alkali metal acetates and especially potassium acetate.

Another preferred group of substances that can be used as ingredient c) are Clay minerals. Natural or chemically modified clay minerals can be used here become. Particularly preferred clay minerals are the bentonites, which are part of the Invention c) are very suitable.  

Bentonites are contaminated clays that are formed by weathering volcanic tuffs. It is possible to adapt the properties of the bentonites to the intended use modify. Bentonites are common as a clay component in tropical soils and are considered Sodium bentonite e.g. B. mined in Wyoming / USA. Sodium bentonite has the cheapest application properties, so that its use in the context of present invention is preferred. Naturally occurring calcium bentonites come from for example from Mississippi / USA or Texas / USA or from Landshut / D. Of course Ca bentonites obtained are artificially replaced by exchanging Ca for Na swellable Na bentonite converted.

The main constituents of bentonites are so-called montmorillonites, which can also be used in pure form in the context of the present invention. Montmorillonites belong to the phyllosilicates and here to the dioctahedral smectites clay minerals that crystallize monoclinic-pseudohexagonal. Montmorillonites predominantly form white, gray-white to yellowish, completely amorphous appearing, easily friable, swelling in the water, but not becoming plastic, by the general formula

Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .nH ₂ O or

Al ₂ O ₃ .4SiO ₂ .H ₂ O.nH ₂ O or

Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] (dried at 150 °)

can be described.

Montmorillonites have a three-layer structure that consists of two tetrahedral layers that are electrostatically cross-linked via the cations of an intermediate octahedral layer. The layers are not rigidly connected, but can be reversibly incorporated by water (in 2-7 times the amount) and other substances such as. As alcohols, glycols, pyridine, α-picoline, ammonium compounds, hydroxy aluminosilicate ions, etc. swell. The above. Formulas are only approximate formulas because montmorillonites have a large ion exchange capacity. Al can be exchanged for Mg, Fe ²⁺ , Fe ³⁺ , Zn, Cr, Cu and other ions. As a result of such a substitution, the layers are negatively charged, which is balanced by other cations, especially Na ⁺ and Ca ²⁺ .

The structure of the phyllosilicates, in which a central layer of octahedrally coordinated cations is sandwiched by 2 layers of [(Si, Al) O ₄ ] tetrahedra, can be varied widely by numerous substitutions in the octahedron layer. In addition to the predominant Al ³⁺ (montmorillonite - dioctahedral layered silicate), the octahedron layer can also contain, for example, Mg ²⁺ (saponite - trioctahedral layered silicate) or Fe ³⁺ (nontronite - dioctahedral layered silicate). It also contains cations such as Zn ²⁺ (for sauconite - trioctahedral sheet silicate), Ni ²⁺ (nickel sauconite - trioctahedral sheet silicate) and Li ⁺ (hectorite - trioctahedral sheet silicate). Substitutions can also be observed in the tetrahedral layer, for example Si ⁴⁺ can be replaced in part by Al ³⁺ (in the case of beidellite - dioctahedral sheet silicate) and also by Fe ³⁺ (in the case of nontronite - dioctahedral sheet silicate). These substitutions result in an imbalance in the charge balance, which is compensated for by interchangeable cations, usually sodium, calcium and potassium, also magnesium, between the layer packs.

The following general formulas can be used for dioctahedral phyllosilicates

(K, Ca, Na, Mg) ^{i +} [Si _4-x (Al, Fe ³⁺ ) _x O ₁₀ ] [(Al, Fe ³⁺ ) _2-y (Mg, Fe ²⁺ ) _{y + z} (OH) ₂ ]

with i = approx. 0.6 to 0.2 per O ₁₀ (OH) ₂ and further i = x + y-2z and for trioctahedral phyllosilicates

(K, Ca, Na, Mg) ^{i +} [Si _4-x (Al _x O ₁₀ ] [(Mg, Fe ²⁺ ) _3-y (Al, Fe ³⁺ ) _yz (OH) ₂ ]

specify with i = x - y + 3z and 0.6 <i <0.2.

In the context of the present invention, bentonites are preferably used in the classic sense, clays with a high montmorillonite content. Preferred ingredient c) are Phyllosilicates with a montmorillonite content of more than 60% by weight, preferably of more than 75 wt .-% and in particular of more than 90 wt .-%, each based on the Weight of the phyllosilicate.  

If this is not undesirable for reasons of cost, preference can also be given to pure ones Insert montmorillonite. Detergent components that are pure as bentonite Montmorillonites are also preferred according to the invention.

The layer spacing of phyllosilicates can be achieved by installing certain compounds modify, as - depending on the charge of the elementary layers and the Interlayer cations - can swell, d. H. the base distance of your three-layer packages by storing water molecules or long-chain organic molecules on over 15 Å can enlarge. According to the invention, chemically modified bentonites can also be used as Ingredient c) are used, with detergent components being preferred which are characterized by quaternary ammonium compounds contain modified bentonites.

Preferred detergent components in the context of the present invention contain as Ingredient c) Substances from the group of clay minerals, preferably chemical ones modified clay minerals and especially the hydrophobized bentonites.

Other solids to be used as ingredient c) in the context of the present invention are ionic surfactants, provided that they have a sufficiently high melting point and can be brought to the particle size range mentioned. These surfactants have been described in detail above. In particular, fatty alcohol sulfates are preferred as ingredient c), so that detergent components are preferred which contain, as ingredient c), anionic surfactant (s), preferably fatty alcohol sulfates and in particular C _12-18 fatty alcohol sulfates.

The detergent components according to the invention can preferably be used as ingredient d) further active substances and / or auxiliary substances from the groups of dyes, fragrances, soil-release Polymers, corrosion inhibitors, enzymes, bleaches, bleach activators and complexing agents in amounts of 0 to 10% by weight, preferably 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. Color and Fragrances and the other substances mentioned are common ingredients of washing or Detergents and are described in detail below.  

As already mentioned above, through a suitable choice of ingredients a) to d) physical and chemical properties of the invention Vary the detergent components in a targeted manner. For example, only ingredients used, which are liquid at the melting temperature of the emulsion, can be easily produce single-phase mixtures that also have special storage stability mark the melted state. The addition of solids, such as Color pigments or substances with higher melting points automatically lead to two-phase Mixtures that are also excellent in storage stability and extremely low Have a tendency to split.

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

At room temperature, the detergent components according to the invention solidify Mixtures of the ingredients mentioned, which can take any external form. It is also possible to apply the mixtures as a melt to carriers and so on To provide carrier material-based detergent components that work at room temperature consist of carrier material (s) and a melt solidified on these carrier materials. As Support materials are all solids that are not at the temperature of the melt soften and also have a sufficiently large absorption capacity for the melt exhibit. Particularly preferred carrier materials are builders, which are further below be described in detail.

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

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20 g / l at 20 ° C,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

applied to one or more carrier materials and the mixture processed shaping.  

In this process variant, a melt suspension or emulsion is used first manufactured, which may contain other active ingredients and auxiliary substances. This is on a carrier material given and processed in a mixture with this carrier material.

In the aforementioned manufacturing process for the invention Detergent components are preferred process variants in which the meltable Substance 25 to 85% by weight, preferably 30 to 70% by weight and in particular 40 to 50% by weight that makes up the melt.

The application of the melt to the carrier material can be done in all usual ways Mixing devices are carried out. The shaping processing step for the Mixture of melt and carrier material is also not subject to any process engineering Restrictions, so that the person skilled in the art can select from the methods familiar to him can. In tests by the applicant, methods have been found to be preferred which the shaping processing by granulating, compacting, pelleting, extruding or tableting.

The method according to the invention comprises the application of melts from the ingredients a) to d) on carrier materials. In principle, the melt and carrier (s) can vary Amounts may be contained in the resulting rinse aid particles. Preferred methods are characterized in that a mixture of 5 to 50 wt .-%, preferably 10 to 45 wt .-%, particularly preferably 15 to 40% by weight and in particular 20 to 35% by weight of a melt from the ingredients a) to d) and 50 to 95% 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 processed to give shape.

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

The detergent components according to the invention can also be free of carrier material be formulated so that they consist only of the ingredients a) to d). For the production  Particulate detergent components according to the invention have been found In particular, the preening, the pastilling and the scaling by means of chill rolls have proven their worth.

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

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20 g / l at 20 ° C,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

injected into a cold gas stream.

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

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

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

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

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20 g / l at 20 ° C,  
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

dosed on chilled pastilles.

Pastilling, which is sometimes referred to as pelleting, includes the dosage of Melt the ingredients a) through d) onto rotating, inclined plates that have a temperature have below the melting temperature of the melt and preferably below Be cooled to room temperature. Process variants can also be carried out here where the pastilles are frozen. However, measures have to be taken against condensation of air humidity.

The pastillation provides larger particles, which are between sizes in the case of technically customary processes Have 2 and 10 mm, preferably between 3 and 6 mm.

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

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20 g / l at 20 ° C,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

apply or spray on a chill roll, scrape off the solidified melt and if crushed required.

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

Of course, it is also possible according to the invention to use the particulate ones Compress compositions to a shaped body or an area thereof. This  Shaped bodies can then be metered by the consumer, for example, but they can also powdery compositions can be added. It is also possible that particulate compositions, especially the prills, pastilles or products of the Cooling roller to be used as a tablettable premix and in the production of to use multi-phase moldings. Here, for example, the compression then delivers multilayer tablets, one layer of which is the composition of a conventional one Detergent tablet, the other layer the composition of the invention Detergent component, which is also advantageous in this form unfolded.

Multi-phase moldings can also be produced by molding with cavities, for example, troughs or through holes, and these cavities are subsequently filled with other moldings. In the present case, it has proven useful that the "base molding", d. H. the tablet, which has a cavity, the composition has a detergent tablet, while the molded body contained in the cavity Shaped body that is pressed from prills, pastilles or scales. The liability of the two Shaped bodies can be achieved by gluing the two shaped bodies together, but it is also possible to press the molded bodies into or into one another. Also the nesting, at which is achieved through the geometrical design of the cavity and filling, is possible.

The production process is, for example, the production of the shaped bodies by separate Production (pressing) of a base molding a) and a core molding b) which is preferably pressed from prills of the detergent components according to the invention, the Joining and the final pressing of both parts, preferred.

The production of moldings from particulate according to the invention Detergent components can be made using standard tabletting processes. These will described in detail below.

The moldings can be made in a predetermined spatial shape and a predetermined size become. Practically all sensibly manageable designs come in as the spatial form Consider, for example, the formation as a board, the rod or bar shape, cubes,  Cuboid and corresponding room elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last one Design covers the presentation form from the tablet to compact Cylinder pieces with a ratio of height to diameter above 1.

The molded body produced can assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, octagonal and octagonal-prismatic as well rhombohedral shapes are preferred. Also completely irregular bases such as arrow or Animal forms, trees, clouds, etc. can be realized. The molded body shows Corners and edges, so they are preferably rounded. As an additional optical Differentiation is an embodiment with rounded corners and beveled ("chamfered") edges preferred.

The detergent components according to the invention can be sent directly to the consumer Hand be given, so that he dosed them in addition to the detergent as needed. Due to this additional dosing step, however, in addition to the fixed form of supply and adding it to the same dosing compartment has the advantages over liquid rinse aid minimized. It is therefore preferred to use the detergent components according to the invention to mix particulate machine dishwashing detergents or these in moldings to incorporate.

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

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20 g / l at 20 ° C,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

in detergents for automatic dishwashing.  

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

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20 g / l at 20 ° C,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

contain.

The ingredients of automatic dishwashing detergents are described below. To the Some of these can also be used as ingredient d) or carrier materials in the inventive Detergent components may be included.

The most important ingredients in automatic dishwashing detergents are builders. In the Detergents according to the invention for machine dishwashing can all be used builders usually used in detergents and cleaning agents, especially zeolites, silicates, carbonates, organic cobuilders and - if none There are ecological concerns about their use - including the phosphates. The below Builders mentioned are all as carrier materials for the inventive Detergent components suitable, as already explained above.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.

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

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

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

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

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. Among the variety of commercially available phosphates are the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or Potassium tripolyphosphate) in the detergent and cleaning agent industry.

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

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

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

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

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

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

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the crystal water-free salt dissolve at room temperature, about 20 g at 60 ° and about 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 O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

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

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or Mixtures of these two can be used; 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.

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

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have 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), provided such use ecological reasons are not objectionable, as well as 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. The acids have besides theirs Builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

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

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. 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 2000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molar masses from 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special  copolymers of acrylic acid with maleic acid which have 50 to 90% by weight have proven suitable Contain acrylic acid and 50 to 10 wt .-% maleic acid. Your molecular weight, based on free acids, is generally from 2000 to 70,000 g / mol, preferably 20,000 up to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The amount 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 allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of acrylic acid as monomers and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers preferably have acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

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

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

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates obtained by partial hydrolysis of starches can. The hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed  Procedures are carried out. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide is included a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a poly saccharids compared to dextrose, which has a DE of 100. Both are usable 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 ones Molar masses in the range from 2000 to 30,000 g / mol.

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

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and are also preferred in this context Glycerol trisuccinate. Suitable amounts are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.

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

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly special Meaning as a cobuilder. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate  (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B. as 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 strong ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, it may be preferred Aminoalkanephosphonate, especially DTPMP to use, or mixtures of the to use the named phosphonates.

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

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

In addition to the builders, there are in particular substances from the groups of surfactants Bleach, bleach activators, enzymes, polymers, colors and fragrances important ingredients of detergents. Important representatives from the above Substance classes are described below, with respect to the description of the Surfactants is referred to the explanations above.

Preferred particulate machine dishwashing detergents further contain one or several substances from the groups of bleaching agents, bleach activators, bleach catalysts, Surfactants, corrosion inhibitors, polymers, colors and fragrances, pH adjusting agents, complexing agents and the enzymes.

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

"Sodium percarbonate" is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not "percarbonates" (ie salts of percarbonic acid), but rather hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ .3 H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which easily decomposes 55222 00070 552 001000280000000200012000285915511100040 0002019957505 00004 55103 in sodium carbonate and bleaching or oxidizing oxygen.

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

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

Cleaning agents according to the invention can also contain bleaches from the group of organic Bleach included. Typical organic bleaches are the diacyl peroxides, such as. B. Dibenzoyl peroxide. Other typical organic bleaching agents are the peroxy acids, where as Examples include the alkyl peroxy acids and the aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as  Alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, Peroxystearic acid, ε-phthalimido-peroxycaproic acid [phthaloiminoperoxyhexanoic 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, diperocysebacic acid, Diperoxybrassylic acid, the diperoxy-phthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N- Terephthaloyl-di (6-aminopercaproic acid) can be used.

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

The bleaches mentioned can also be used in part to achieve "post-bleaching" Detergent components according to the invention, where they represent the ingredient d), in the machine dishwashing detergents according to the invention are introduced.

Bleach activators that support the action of the bleach are, for example Compounds that 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 tetraacetylethylene diamine TAED, tetraacetyl methylene diamine TAMD and Tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used. Are suitable Substances containing O and / or N-acyl groups with the number of carbon atoms mentioned and / or against also carry substituted benzoyl groups. Multi-acylated alkylene are preferred  diamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular their 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, esp special tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesul fonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5- dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (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 their mixtures (SORMAN) Sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated, glucamine and gluco nolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilic sub substituted acylacetals and acyllactams are also preferred. Also Combinations of conventional bleach activators can be used.

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

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

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 the cobalt (ammin) complexes, the  Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or Manganese, the manganese sulfate are in usual amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in In special cases, more bleach activator can be used.

In the cleaning agents according to the invention, the enzymes in particular come from Classes of hydrolases such as proteases, esterases, lipases or lipolytic Enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains. Oxidoreductases can also be used for bleaching. Bacterial strains or fungi such as Bacillus subtilis or Bacillus are particularly suitable licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified variants obtained enzymatic active ingredients. Preferably are proteases of the subtilisin type and in particular proteases derived from Bacillus lentus won, used. Enzyme mixtures, for example of protease and Amylase or protease and lipase or lipolytically active enzymes or from protease, Amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic acting enzymes, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. examples for Such lipolytic enzymes are the well-known cutinases. Peroxidases or Oxidases have been found to be suitable in some cases. To the suitable amylases count in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

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

Dyes and fragrances can be used in the dishwasher detergents according to the invention can be added to improve the aesthetic impression of the resulting products and the consumer in addition to the performance a visually and sensory "typical and to provide a distinctive "product. Can be used as perfume oils or fragrances  individual fragrance compounds, e.g. B. the synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p- tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. B. the linear alkanals with 8-18 C atoms, citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, among the Ketones e.g. B. the Jonone, α-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol Hydrocarbons mainly belong to the terpenes like limonene and pinene. Prefers however, mixtures of different odoriferous substances are used, which together form a generate an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures contain as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and 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, however, it can also be advantageous to apply the fragrances to carriers. As such Carrier materials have proven themselves, for example, cyclodextrins, the cyclodextrin Perfume complexes can also be coated with other auxiliaries. Also an incorporation of the fragrances as ingredient d) in the invention Detergent components are possible and lead to a scent impression when opening the Machine.

In order to improve the aesthetic impression of the agents according to the invention, it (or parts of which) are dyed with suitable dyes. Preferred dyes, their selection the expert has no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agents and to light and none pronounced substantivity towards the substrates to be treated with the agents such as glass, Ceramics or plastic dishes so as not to stain them.  

The cleaning agents according to the invention can protect the dishes or the machine Contain corrosion inhibitors, especially silver protection agents in the area of automatic dishwashing have a special meaning. The known ones can be used State of the art substances. In general, silver protection agents can be selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Alkylaminotriazoles and the transition metal salts or complexes are used. Especially benzotriazole and / or alkylaminotriazole are preferred. One finds in In addition, detergent formulations often contain active chlorine agents that corrode the Can significantly reduce the silver surface. Chlorine-free cleaners are special Oxygen and nitrogen-containing organic redox-active compounds, such as two and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred are the transition metal salts that are selected are particularly preferred from the group of manganese and / or cobalt salts and / or complexes the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. You can also Zinc compounds are used to prevent corrosion on the wash ware.

The particulate machine dishwashing detergents according to the invention can Contain detergent components according to the invention in varying amounts, the Content depending on the composition of the detergent components and the desired Application success is higher or lower. Preferred particulate machine Dishwashing detergents contain the particulate detergent component in amounts of 0.5 to 30% by weight, preferably from 1 to 25% by weight and in particular from 3 to 15% by weight, in each case based on the total mean.

The detergent components according to the invention can have a composition be designed so that they are in the main wash cycle (and also in optional pre-wash cycles) not or only to a minor extent. This ensures that the surfactants only are released in the rinse aid and develop their effect here. In addition to this chemical Depending on the type of dishwasher, assembly is a physical assembly  required so that the rinse aid particles do not drain out when the water is changed in the machine and are therefore no longer available for the rinse aid. Common household Dishwashers contain before the drain pump, which the water or Pumps cleaning solution out of the machine after each cleaning cycle, one Sieve insert, which is intended to prevent the pump from becoming blocked by dirt residues. Will be from If heavily soiled dishes are washed by consumers, this strainer must be used regularly can be cleaned, which is easy due to the easy accessibility and removable is possible. The detergent components according to the invention are now in terms of their Size and shape preferably designed so that they the sieve insert of the dishwasher even after the cleaning cycle, d. H. after exposure to movement in the machine and the Cleaning solution, do not happen. In this way it is ensured that in Rinse aid detergent components are in the dishwasher, which release the active substance (s) under the influence of the warmer water and the bring the desired rinse aid effect. Preferred in the context of the present invention Particulate machine dishwashing detergents are characterized in that the particulate detergent component 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 can also be used the aforementioned sizes from the matrix of the other particulate ingredients protrude, but the other particles can also have sizes that in the above Range, so that a total of a detergent is formulated, which consists of large Detergent and detergent component particles exist. Especially if the detergent components according to the invention are colored, for example one red, blue, green or yellow in color, it is for the appearance of the product, i. H. of the entire cleaning agent is an advantage if the cleaning agent components are visible are 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) particle sizes between 100 and 6000 µm, preferably up to 4500 µm and in particular between 100 and 3000 µm have, especially particle sizes between 300 and 2500 microns and in particular between 400 and 2000 microns are particularly preferred.  

If the cleaning agents according to the invention are formulated as a powder mixture, especially with very different sizes of detergent components and Detergent matrix - partial segregation when the package is shaken occur, on the other hand, the dosage in two successive cleaning cycles be different since the consumer does not always necessarily have the same amount of detergent and Detergent component dosed. Should be desired, technically always the same To use the amount per cleaning cycle, this can be done via the one familiar to the person skilled in the art Packaging of the agents according to the invention in bags made of water-soluble film become. Also a particulate machine dishwashing detergent, which is characterized is that a dosing unit is sealed in a bag made of water-soluble film an object of the present invention.

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

Because the consumer is not just particulate cleaners for the machine Uses dishwashing, but also wants to use molded articles, these are one further object of the present invention. For this purpose, the melt from the Formulate ingredients a) to d) as a phase of a shaped body, for example the shape a layer, a core-shaped insert, etc.

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

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20 g / l at 20 ° C,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

consists.  

The individual phases of the shaped body can be within the scope of the present invention have different spatial shapes. The simplest possible implementation is in two- or multi-layer tablets, each layer of the shaped body representing a phase. However, it is also possible according to the invention to produce multiphase molded articles in which individual phases have the form of inclusions in another phase (s). Next So-called "ring core tablets" are, for example, coated tablets or Combinations of the mentioned embodiments are possible. Examples of multiphase Shaped bodies can be found in the illustrations of EP-A-0 055 100 (Jeyes), the Toilet cleaning blocks describes. The currently most widespread spatial form Multi-phase tablet is the two- or multi-layer tablet. As part of the present According to the invention, it is therefore preferred that the phases of the shaped body take the form of layers have and the molded body is 2-, 3- or 4-phase.

The moldings according to the invention can take on any geometric shape, wherein in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, hexagonal and octagonal prismatic as well rhombohedral shapes are preferred. Also completely irregular bases such as arrow or Animal forms, trees, clouds, etc. can be realized. Assign the inventive Shaped body corners and edges, they are preferably rounded. As an additional optical differentiation is an embodiment with rounded corners and beveled ("chamfered") edges preferred.

Instead of the layer structure, it is also possible to produce moldings which are the inventive ones Include detergent component in the form of other phases. It has proven itself here To produce base moldings which have one or more cavity (s) and which Melt from the ingredients a) to d) of the detergent component according to the invention pour into the cavity and allow to solidify there. Through this manufacturing process preferred multi-phase detergent tablets result from a Basic molded body, which has a cavity, and one at least partially in the cavity contained part exist.  

The cavity in the pressed part of such shaped bodies according to the invention can be any Have shape. You can cut through the molded body, d. H. an opening at different Have sides, for example on the top and bottom of the molded body, but it can also a cavity that does not go through the entire molded body, the opening of which is only on one Shaped body side is visible. The shape of the cavity can also be freely selected within wide limits become. For reasons of process economy, there are continuous holes in them Openings lie on opposite surfaces of the molded body, and troughs with an opening on one side of the molded body has proven itself. In preferred washing and Detergent tablets have the shape of a through hole, the openings of which are located on two opposing shaped body surfaces. Form such a through hole can be chosen freely, with molded bodies being preferred in which the through hole is circular, elliptical, triangular, rectangular, has square, pentagonal, hexagonal, heptagonal or octagonal horizontal sections. Completely irregular hole shapes such as arrow or animal shapes, trees, clouds etc. can also be used will be realized. As with the shaped bodies, in the case of angular holes, such are also included rounded corners and edges or with rounded corners and chamfered edges preferred.

The geometric implementation forms mentioned above can be combined with one another as desired combine. Shaped bodies with a rectangular or square base and circular holes are produced as well as round shaped bodies with octagonal holes, whereby there are no limits to the variety of possible combinations. Because of Process economics and aesthetic consumer perception are molded articles with holes particularly preferred in which the shaped body base area and the hole cross section are the same have geometric shape, for example shaped bodies with a square base area and central incorporated square hole. Ring moldings are particularly preferred, i. H. circular shaped body with a circular hole.

If the above Principle of the hole open on two opposite sides of the molded body on one Opening is reduced, mold bodies are obtained. Washing and Detergent tablets in which the cavity has the shape of a trough also preferred. As with the "hole moldings", the inventive Shaped bodies also assume any geometric shape in this embodiment, wherein in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic,  cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, hexagonal and octagonal prismatic as well rhombohedral shapes are preferred. Also completely irregular bases such as arrow or Animal forms, trees, clouds, etc. can be realized. If the molded body has corners and Edges on, so these are preferably rounded. As an additional optical differentiation an embodiment with rounded corners and beveled ("chamfered") edges prefers.

The shape of the trough can also be chosen freely, preference being given to moldings in which at least one trough a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, hexagonal and octagonal prismatic as well rhombohedral shape can take. Completely irregular trough shapes such as arrow or Animal forms, trees, clouds, etc. can be realized. As with the shaped bodies Troughs with rounded corners and edges or with rounded corners and chamfered Edges preferred.

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

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20 g / l at 20 ° C,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

consists.

The size of the trough or through hole compared to the entire molded body depends on the intended use of the molded body. Whichever, with how much more active substance the remaining void volume should be filled and whether one Lesser or greater amount of detergent component should be included  The size of the cavity vary. Regardless of the intended use, washing and Preferred detergent tablets, in which the volume ratio of the pressed part ("Base molding") for detergent component 2: 1 to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1.

In addition to the volume ratio mentioned, a mass ratio of the two parts can also are specified, the two values relating to the densities of the base molding and the Correlate detergent components with each other. Regardless of the density of each Parts of detergent tablets according to the invention are preferred in which the Weight ratio of base molding to detergent component 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1 is.

Analogous information can also be given for the surfaces, each of which Base moldings or from the detergent component are visible. Here are washing or Preferred detergent tablets, in which the outwardly visible surface of the Detergent component 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular accounts for 4 to 10% of the total surface of the molded body.

The detergent component and the base molding are preferably optical distinctively colored. In addition to the optical differentiation, application technology Advantages achieved through different solubilities of the different shaped body regions become. Detergent tablets in which the Detergent components dissolve faster than the base molding, are according to the invention prefers. By incorporating certain components, the solubility of the Detergent components can be specifically accelerated, on the other hand, the release certain ingredients from the detergent component for advantages in washing or Carry out cleaning process.

Of course, detergent tablets according to the invention are also molded preferred, in which the detergent component dissolves later than the base molding. Performance advantages from this delayed release can be achieved, for example achieve that with the help of a slower soluble detergent component  Active substance (s) are only released in later rinses. For example, at machine dishwashing achieved by detergent components that dissolve more slowly that additional active substance (s) is / are available in the rinse aid cycle. By additional substances such as nonionic surfactants, acidifying agents, soil release polymers etc. the rinse aid results can be improved in this way. There is also an incorporation of perfume possible without any problems; due to its delayed release, the "Lye smell" that often occurs when opening the machine can be eliminated. The ingredients Acidifiers, soil release polymers, etc. are based on the inventive ones Detergent components then sourced ingredients d).

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

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

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

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, each based on the weight of the molded body. Contains only the basic tablet Disintegration aids, the information given relates only to the weight of the Basic molded body. When incorporating disintegration aids into the Detergent components according to the invention include those as ingredient d).

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

The cellulose used as disintegration aid is preferably not in finely divided form Form, but before mixing into the premixes to be pressed into a transferred coarser form, for example granulated or compacted. Washing and  Detergent tablets, the disintegrants in granular or optionally co-granulated Form contained, are in the German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and international patent application WO 98/40463 (Henkel) described. These documents also contain more information on the production of granulated, compacted or cogranulated cellulose disintegrant. The particle sizes 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 aforementioned and described in more detail in the cited documents Coarser disintegration aids based on cellulose are within the scope of the present Invention preferably used as a disintegration aid and commercially, for example available under the name Arbocel® TF-30-HG from Rettenmaier.

As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is made by partial hydrolysis of celluloses obtained under such conditions that only the amorphous Attack areas (approx. 30% of the total cellulose mass) of the celluloses and completely dissolve, but leave the crystalline areas (approx. 70%) undamaged. A subsequent one The disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses with primary particle sizes of approx. 5 µm and for example, can be compacted into granules with an average particle size of 200 μm.

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

The detergent tablets according to the invention can moreover both in Basic molded body as well as a gas-developing in the detergent component Shower system included. The gas-developing shower system can consist of a single substance exist, which releases a gas on contact with water. Among these connections is especially magnesium peroxide, which releases oxygen on contact with water. Usually, however, the gas-releasing bubble system itself consists of at least two  Ingredients that react with each other to produce gas. While here a variety of Systems are conceivable and executable, for example nitrogen, oxygen or hydrogen liberate that will in the detergent tablets according to the invention bubble system used both on the basis of economic and ecological Have aspects selected. Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable from the Release alkali metal salts in aqueous solution carbon dioxide.

The alkali metal carbonates and bicarbonates are the sodium and potassium salts clearly preferred over the other salts for cost reasons. Needless to say the pure alkali metal carbonates or bicarbonates concerned are not used; rather, mixtures of different carbonates and hydrogen carbonates can be formed washing technology be preferred.

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 to 10 wt .-% an acidifying agent, based in each case on the entire molded body.

As an acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution, are, for example, boric acid and alkali metal bisulfates, Alkali metal dihydrogen phosphates and other inorganic salts can be used. To be favoured however, organic acidifiers are used, with citric acid being a particular preferred acidifying agent. However, the other fixed ones can also be used in particular Mono-, oligo- and polycarboxylic acids. From this group tartaric acid is preferred, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well Polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as an acidifying agent in the context of the present invention Sokalan® DCS (trademark of BASF), a mixture of Succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).  

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

The particulate detergents and / or detergent tablets can - like the detergent components per se - be packaged after manufacture, the use of certain packaging 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) detergent tablet (s) according to the invention and a packaging system containing the cleaning agent and / or the detergent tablet (s), wherein the packaging system has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

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

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

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

The relative equilibrium humidity of 85% at 23 ° C can be found, for example, in Laboratory chambers with humidity control to +/- 2% r. Depending on the device type. Adjust L. exactly. Closed systems also form over saturated solutions of certain salts given temperature constant and well-defined relative humidity levels on the Phase equilibrium between the partial pressure of water, saturated solution and soil are based.

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

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

The packaging system of the combination according to the invention encloses depending on Embodiment of the invention a certain amount of inventive Detergent component, a certain amount of a particulate Detergent composition or one or more washing and Detergent tablets. It is preferred according to the invention, either one To design shaped body so that it is an application unit of the washing and Detergent includes, and to package this molded article individually, or the number To pack molded articles in a packaging unit, which in total is one application unit includes. So it is with a nominal dosage of 80 g of detergent and cleaning agents possible according to the invention, a 80 g heavy detergent tablet to produce and pack individually, but it is also possible according to the invention, two 40 g each to pack heavy detergent tablets into a packaging in order to form a combination to arrive. This principle can be taken for granted expand, so that combinations according to the invention also three, four, five or even more washing and can contain detergent tablets in a packaging unit. Of course, two or more molded articles can be different in one package Have compositions. This way it is possible to have certain components to separate them spatially from each other, for example to avoid stability problems.

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

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

The sacks or bags made of one layer, which are preferably to be used as a packaging system or laminated paper or plastic film can be made in many different ways be designed, for example as a blown bag without a central seam or as a bag with Middle seam, which is closed by heat (hot melt), adhesives or adhesive tapes become. Single-layer bag or sack materials are the known papers that can optionally be impregnated, and plastic films, which if necessary can be coextruded. Plastic films that in the present invention as Packaging system can be used, for example, in Hans Domininghaus "Die Plastics and their properties ", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193, specified. Fig. 111 shown there also provides clues Water vapor permeability of the materials mentioned.

Combinations 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 up to 50 µm.

Although it is possible, wax-coated in addition to the films or papers mentioned Papers in the form of cardboard packaging systems for washing and To use detergent tablets, it is within the scope of the present invention preferred if the packaging system does not include boxes of wax coated paper. The term "packaging system" characterizes in the context of the present invention always the primary packaging of the detergent component, Detergent composition or molded article, d. H. the packaging on your Inside directly with the detergent component, detergent composition or Molded surface is in contact. There is no need for an optional secondary packaging  Requirements, so that all common materials and systems are used here can.

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

The relative equilibrium moisture content of the detergent and Detergent tablets can be determined according to common methods, in which The following procedure was chosen within the scope of the present investigations: 1 liter water-tight container with a lid, which has a closable opening for the introduction of samples, was washed with a total of 300 g Detergent tablets filled and kept at a constant 23 ° C for 24 h to ensure a uniform Ensure the temperature of the vessel and substance. The water vapor pressure in the room above the moldings can then be cleaned with a hygrometer (Hygrotest 6100, Testoterm Ltd., England) be determined. The water vapor pressure is now measured every 10 minutes to two successive values show no deviation (equilibrium moisture). The above Hygrometer allows a direct display of the recorded values in% relative humidity.

Embodiments of the combination according to the invention in which the packaging system is designed to be resealable. Combinations where the Packaging system has a microperforation can be preferred according to the invention realize.

As mentioned above, detergent components, Detergent compositions or detergent tablets for the machine Manufacture dishwashing according to the inventive method. Accordingly, is a Cleaning process for cleaning dishes in a dishwasher, thereby characterized in that one or more particulate (s) according to the invention  Detergents and / or one or more washing or inventive Detergent tablets insert the dosing chamber of the dishwasher and a washing program can run in the course of which the dosing chamber opens and the cleaning agent or cleaning agents and / or the shaped body or bodies are dissolved, a further subject of the present Invention.

The metering chamber can also be dispensed with in the cleaning process according to the invention and the detergent components according to the invention or Detergent compositions or the shaped article (s) according to the invention place in the cutlery basket, for example. Of course, use is also here a dosing aid, for example a basket, which is attached in the wash cabinet, without any problems possible. Accordingly, a cleaning process for cleaning dishes in one Dishwasher, characterized in that one or more (s) according to the invention particulate cleaning agent and / or one or more washing agents according to the invention or detergent tablets with or without dosing aid in the dishwasher's wash cabinet inserted and runs a rinse program, in the course of which the cleaning agent or cleaning agents and / or the shaped body or bodies are dissolved, a further subject of the present Invention.

Examples

Melt dispersions or emulsions of the following composition [% by weight] were produced:

For this purpose, the nonionic surfactant was heated to 85 ° C., the paraffin was added with stirring and the other ingredients added last. The stability of the suspension / emulsion was at 85 ° C evaluated by switching off the stirrer and visual assessment.

The following scheme was used:
++ visible separation takes place from <60 s
+ visible separation occurs from <30 s
- visible separation takes place from <30 s
- - Visible separation takes place after switching off the stirrer <10 s

The following table shows the results

Claims (40)

1. Detergent component containing

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C. and a water solubility of less than 20 g / l at 20 ° C.,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

with the proviso that at least 90% by weight of the particles c) have particle sizes below 300 µm. 2. Detergent component according to claim 1, characterized in that it as Ingredient a) 15 to 80, preferably 20 to 70, particularly preferably 25 to 60 and contains in particular 30 to 50% by weight of surfactant (s). 3. Detergent component according to one of claims 1 or 2, characterized in that that as ingredient b) 15 to 85, preferably 20 to 80, particularly preferably 25 to 75 and in particular contains 30 to 70% by weight of meltable substance (s). 4. Detergent component according to one of claims 1 to 3, characterized in that they contain the ingredient c) in amounts of 0.15 to 12.5, preferably 0.2 to 10, contains particularly preferably from 0.25 to 7.5 and in particular from 0.3 to 5% by weight. 5. Detergent component according to one of claims 1 to 4, characterized in that it contains, as ingredient a) anionic and / or nonionic surfactant (s), preferably contains nonionic surfactant (s). 6. Detergent component according to one of claims 1 to 5, characterized in that 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 contains in particular between 26.6 and 43.3 ° C.   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 _6-20 - monohydroxyalkanols or C _6-20 alkylphenols or C _{16- 20} fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was obtained. 8. detergent component according to one of claims 1 to 7, characterized in that they contain as ingredient a) ethoxylated and propoxylated nonionic surfactants, in which the Propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant make up contains. 9. Detergent component according to one of claims 1 to 8, characterized in that it contains 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. 10. Detergent component according to one of claims 1 to 9, characterized in that it contains, as ingredient a) end-capped poly (oxyalkylated) nonionic surfactants of the formula
R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²
contains, in which R ¹ and R ^{2 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, iso-propyl , n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type
R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² ,
in which x represents 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 that as ingredient h) 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. 12. Detergent component according to one of claims 1 to 11, characterized in that that as ingredient b) at least one paraffin wax with a melting range of 30 ° C. contains up to 65 ° C. 13. Detergent component according to one of claims 1 to 12, characterized in that that the water solubility of the ingredient b) at 20 ° C less than 15 g / l, preferably less than 10 g / l, particularly preferably less than 5 g / l and in particular less than 2 g / l is. 14. Detergent component according to one of claims 1 to 13, characterized in that at least 90 wt .-% of the particles of c) particle sizes below 190 microns, preferably Have less than 175 microns and especially less than 150 microns. 15. Detergent component according to one of claims 1 to 14, characterized in that the ingredient c) completely from particles with particle sizes below 200 microns, preferably below 175 µm, particularly preferably below 150 µm and in particular below 100 µm, consists. 16. Detergent component according to one of claims 1 to 15, characterized in that they are preferred as ingredient c) alkali metal salts of organic acids Contains alkali metal acetates and especially potassium acetate.   17. Detergent component according to one of claims 1 to 15, characterized in that that as ingredient c) substances from the group of clay minerals, preferably the chemically modified clay minerals and especially the hydrophobized bentonites, contains. 18. Detergent component according to one of claims 1 to 15, characterized in that it contains as the ingredient c) anionic (s) surfactant (s), preferably fatty alcohol sulfates and in particular C _12-18 fatty alcohol sulfates. 19. Detergent component according to one of claims 1 to 18, characterized in that they contain, as ingredient d), further active substances and / or auxiliary substances from the groups of dyes, Fragrances, soil-release polymers, corrosion inhibitors, enzymes, bleach, Bleach activators and complexing agents in amounts of 0 to 10% by weight, preferably of 0.25 to 7.5% by weight, particularly preferably 0.5 to 5% by weight and in particular 0.75 up to 2.5% by weight. 20. Detergent component according to one of claims 1 to 19, characterized by a melting point between 50 and 80 ° C, preferably between 52.5 and 75 ° C and especially between 55 and 65 ° C. 21. A process for the production of particulate detergent components, characterized in that a melt from

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C. and a water solubility of less than 20 g / l at 20 ° C.,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active substances and / or auxiliaries

applied to one or more carrier materials and the mixture processed shaping. 22. The method according to claim 21, characterized in that the shaping processing by granulating, compacting, pelleting, extruding or tableting.   23. A process for the production of prilled detergent components, characterized in that a melt is formed

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C. and a water solubility of less than 20 g / l at 20 ° C.,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

injected into a cold gas stream. 24. A process for the production of detergent components, characterized in that a melt is formed

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C. and a water solubility of less than 20 g / l at 20 ° C.,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

dosed on chilled pastilles. 25. A process for the production of particulate detergent components, characterized in that a melt from

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C. and a water solubility of less than 20 g / l at 20 ° C.,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

applied or sprayed onto a chill roll, scraped off the solidified melt and, if necessary, shredded. 26. Use of particulate detergent components

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C. and a water solubility of less than 20 g / l at 20 ° C.,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

in detergents for automatic dishwashing. 27. Particulate machine dishwashing detergent, containing builders and optionally further detergent ingredients, characterized in that it contains particulate detergent components, based on their weight,

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C. and a water solubility of less than 20 g / l at 20 ° C.,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

contain. 28. Particulate dishwasher detergent according to claim 27, characterized characterized in that it contains builders in amounts of 20 to 80% by weight, preferably 25 up to 75% by weight and in particular from 30 to 70% by weight, in each case based on the weight of the agent. 29. Particulate machine dishwashing detergent according to one of claims 27 or 28, characterized in that it also contains one or more substances from the groups of Bleaching agents, bleach activators, bleaching catalysts, surfactants, corrosion inhibitors, Contains polymers, dyes and fragrances, pH adjusting agents, complexing agents and the enzymes. 30. Particulate dishwasher detergent according to one of claims 27 to 29, characterized in that it contains the particulate detergent component in quantities from 0.5 to 30% by weight, preferably from 1 to 25% by weight and in particular from 3 to 15% by weight, in each case based on the total mean. 31. Particulate dishwasher detergent according to one of claims 27 to 30, characterized in that the particulate detergent component Particle sizes between 1 and 40 mm, preferably between 1.5 and 30 mm and in particular between 2 and 20 mm.   32. Particulate dishwasher detergent according to one of claims 27 to 31, characterized in that it (without taking into account the particulate Detergent component) particle sizes between 100 and 3000 microns, preferably between 300 and 2500 microns and in particular between 400 and 2000 microns. 33. Particulate dishwasher detergent according to one of claims 27 to 32, characterized in that a dosing unit in a bag made of water-soluble film is welded in. 34. Multi-phase detergent tablets for automatic dishwashing, containing builders and optionally further detergent ingredients, characterized in that at least one phase consists of

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C. and a water solubility of less than 20 g / l at 20 ° C.,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

consists. 35. Multi-phase detergent tablet according to claim 34, characterized in that the phases have the form of layers and the shaped body is 2-, 3- or 4-phase. 36. Multi-phase detergent tablet according to claim 34, characterized in that it consists of a base body, which has a cavity, and an at least partially part contained in the cavity. 37. Multi-phase detergent tablet according to claim 36, characterized in that the part contained in the cavity

• a) 10 to 89.9% by weight of surfactant (s),
• b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C. and a water solubility of less than 20 g / l at 20 ° C.,
• c) 0.1 to 15% by weight of one or more solids,
• d) 0 to 15% by weight of further active ingredients and / or auxiliaries

consists. 38. Combination of (a) particulate cleaning agent (s) according to one of claims 24 to 30 and / or (a) detergent or cleaning agent shaped body (s) according to one of claims 31 to 34 and one of the cleaning agent and / or the or the washing Packaging system containing detergent tablets, characterized in that the packaging system has a moisture vapor permeability rate of 0.1 g / m ² / day to less than 20 g / m ² / day if the packaging system is at 23 ° C and a relative equilibrium moisture content of 85%. is stored. 39. Cleaning process for cleaning dishes in a dishwasher, thereby characterized in that one or more particulate detergent (s) according to a of claims 24 to 30 and / or one or more washing or Detergent tablets according to one of claims 31 to 34 in the metering chamber Insert dishwasher and run a washing program, in the course of which the Dosing chamber opens and the cleaning agent (s) and / or the molding (s) be resolved. 40. Cleaning process for cleaning dishes in a dishwasher, thereby characterized in that one or more particulate detergent (s) according to a of claims 24 to 30 and / or one or more washing or Detergent tablets according to one of claims 31 to 34 with or without metering aid put in the dishwasher's wash cabinet and run a wash program in which Course the or the cleaning agent and / or the or the molded body can be dissolved.