EP1803801A1 - Powder or granulate based on glutamic-N,N,diacetic acid and its salts - Google Patents

Abstract

Powder- or granulate mixture comprises (a) 5-95 wt.% of glutamic acid-N,N-acetic acid and/or their salts (I) of formula (MOOC-(CH 2)-2C(COOM)-N(CH 2COOM) 2) with significant alkali metal (MH, NH 4) and (b) 5-95 wt.% of at least a polyethylene glycol, at least a non-ionic surfactant or its mixture or polymers such as polyvinyl alcohols, polyvinylpyrrolidone, polyalkylene glycol and/or its derivatives. Independent claims are included for: (1) a procedure for the production of powder- or granulate mixture comprising mixing the components (a) and (b) in a solvent and spray drying, where further the mixture can be granulated; (2) a solid detergent/dishwashing agent comprising the powder- or granulated mixture and optionally at least a surfactant; and (3) an agent in powder- or granulated form.

Description

The invention relates to a mixed powder or mixed granules based on glutamic acid-N, N-diacetic acid or their salts.

For the preparation of detergents, in particular laundry detergents, or cleaning agents, in particular dishwashing detergents, solid or liquid formulations can be selected. Solid formulations may be present, for example, as powders or granules. The preparation of individual powder or granular detergent ingredients or ingredient mixtures may be difficult or impossible depending on the nature of the ingredients. The powder or granules must not cake together during preparation, mixing and storage of the means and should not affect the spreading or flowability of the powder or granules.

The use of chelating agents in detergents in solid form is known. The WO 95/29216 relates to detergent powder compositions containing a metal ion-chelate complex and an anionic functionalized polymer. The detergent powder contains a complex of a chelating agent and a metal ion selected from magnesium, calcium, strontium, zinc and aluminum as well as a polymer having in particular carboxyl groups. The powder is prepared by spray drying. The chelating agents may be selected from a variety of compounds, glutamic acid-N, N-diacetic acid and their salts are not mentioned. Among the useful polymers are listed polycarboxylates containing water-soluble salts of homo- and copolymers of aliphatic carboxylic acids.

Also the EP-A-0 618 289 relates to highly active granular detergent compositions containing chelates and polymers. The composition comprises an anionic surfactant, a chelating agent and a polymer or copolymer. Again, the chelating agents may be selected from a variety of compounds. However, glutamic acid-N, N-diacetic acid and its salts are not listed. Among the polymers, in particular polycarboxylates such as polyacrylates are listed.

The object of the present invention is to provide mixed powders or mixed granules containing glutamic acid-N, N-diacetic acid or mixed salts thereof for use in solid detergents and cleaners. In particular, the bulk and flowability of the powder or granules should be preserved.

1. (a) 5 bis 95 Gew.-% Glutaminsäure-N,N-diessigsäure und/oder ein oder mehrere ihrer Salze der allgemeinen Formel (I)
   
            MOOC-(CH₂)₂-C(COOM)-N(CH₂COOM)₂     (I)
   
   mit der Bedeutung

   M

   H, NH₄, Alkalimetall

2. (b) 5 bis 95 Gew.-% mindestens eines Polyethylenglykols oder mindestens eines nichtionischen Tensids oder einer Mischung davon oder eines Polymers ausgewählt aus der Gruppe bestehend aus Polyvinylalkoholen, Polyvinylpyrrolidonen (PVP), Polyalkylenglykolen und Derivaten davon.

The object is achieved by a mixed powder or mixed granules containing at least 80 wt .-% of a mixture of

1. (a) 5 to 95% by weight of glutamic acid N, N-diacetic acid and / or one or more of its salts of general formula (I)
   
   MOOC- (CH ₂ ) ₂ -C (COOM) -N (CH ₂ COOM) ₂ (I)
   
   with the meaning

   M

   H, NH ₄ , alkali metal

2. (B) 5 to 95 wt .-% of at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof or a polymer selected from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones (PVP), polyalkylene glycols and derivatives thereof.

The remaining amount can be accounted for by other auxiliaries, such as conventional detergent additives or fillers. The mixture preferably consists essentially, more preferably only of components (a) and (b).

In one embodiment, the mixture contains as component (b) 5 to 95 wt .-% of at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof.

It has been found according to the invention that a combination of alkali metal salts of glutamic acid-N, N-diacetic acid with at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof or a polymer selected from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones (PVP), polyalkylene glycols and derivatives resulting in powders or granules, which have a low hygroscopicity and a good storage behavior and thus can be used advantageously in solid detergents and cleaners. The funds are very stable on storage and even after long periods still pourable and pourable.

in der

M

Wasserstoff, Ammonium oder Alkalimetall bedeuten.

Suitable glutamic acid N, N-diacetic acid and its salts are accordingly compounds of the general formula (I)

in the

M

Mean hydrogen, ammonium or alkali metal.

In the compounds of the general formula (I), M is hydrogen (H), ammonium (NH ₄ ) or an alkali metal (eg Li, Na.K,), preferably sodium or potassium, more preferably sodium.

Component (b) used is at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof or a polymer selected from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones (PVP), polyalkylene glycols and derivatives thereof.

As component (b) is preferably used a polyethylene glycol, more preferably having an average molecular weight (weight average molecular weight) of 500 to 30,000 g / mol.

In a preferred embodiment, the polyethylene glycol used as component (b) has OH end groups and / or C _1-6 -alkyl end groups. In the mixture according to the invention it is particularly preferred to use as component (b) a polyethylene glycol which has OH and / or methyl end groups.

Preferably, the polyethylene glycol used in the mixture according to the invention has a molecular weight (weight average molecular weight) of 1000 to 5000 g / mol, most preferably from 1200 to 2000 g / mol.

As suitable compounds, nonionic surfactants can be used as component (b). These are preferably selected from the group consisting of alkoxylated, primary alcohols, alkoxylated fatty alcohols, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides and polyhydroxy fatty acid amides.

As nonionic surfactants are preferably alkoxylated, preferably 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 used, in which the alcohol radical may linear or preferably methyl-branched in the 2-position or may contain linear and branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, are alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols containing 3 EO, 4 EO or 7 EO, C _9-11 alcohols 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 of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-14 -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means that may be a whole or fractional number for a particular 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 alcohols with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units, or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) can be used, in which R is a primary straight-chain or methyl-branched especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G the symbol is that which represents a glycose unit having 5 or 6 C atoms, preferably glycose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

Nonionic surfactants of the amine oxide type, for example N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

in der RC=O für einen aliphatischen Acylrest mit 6 bis 22 C-Atomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 C-Atomen und (Z) für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 C-Atomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further nonionic surfactants are polyhydroxy fatty acid amides of the formula (II)

in the RC = O for an aliphatic acyl radical having 6 to 22 C atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 C atoms and (Z) for a linear or branched polyhydroxyalkyl radical having 3 to 10 C 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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 C-Atomen, R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 C-Atomen und R³ für H, einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 C-Atomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und (Z) für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte, Derivate dieses Restes. (Z) wird vorzugsweise durch reduktive Aminierung eines Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 C atoms, R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 C atoms and R ^{3 is} H, a linear, branched or a cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 C atoms, where C _1-4 -alkyl or phenyl radicals are preferred and (Z) is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups , or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this group. (Z) is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Low-foaming, nonionic surfactants are preferably used which have a melting point above room temperature. Accordingly, preferred blends are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably from 25 to 100 ° C, and most preferably from 30 to 50 ° C , contain.

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

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

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 mol, ethylene oxide per mole of alcohol or alkylphenol emerged.

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

Accordingly, particularly preferred mixtures according to the invention comprise ethoxylated (s), nonionic surfactant (s) which are prepared from 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 was recovered (n).

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes more than 30 wt .-%, more preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total molecular weight of such nonionic surfactants. Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of nonionic surfactant.

Further particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight % of a block 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.

The mixture according to the invention contains as another preferred nonionic surfactant a compound of the formula (IV)

R ⁴ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ⁵ (IV)

in which R ^{4 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 C atoms or mixtures thereof, R ⁵ denotes a linear or branched hydrocarbon radical having 2 to 26 C atoms or mixtures thereof, and x for values of 0.5 to 1.5 and y stands for a value of at least 15.

Further preferably usable nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula (V)

R ⁶ O [CH ₂ CH (R ⁸ ) O] _z [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ⁷ (V)

in which R ⁶ and R ^{7 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 C atoms, R ^{8 is} hydrogen or a methyl, ethyl, n-propyl, iso-propyl, n is -butyl, 2-butyl or 2-methyl-2-butyl, z is from 1 to 30, k and j are from 1 to 12, preferably from 1 to 5. When the value z ≥ 2, each R ⁸ in formula (V) may be different. R ⁶ and R ⁷ are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ⁸ , hydrogen, methyl or ethyl are particularly preferred. Particularly preferred values for z are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ⁸ in formula (V) may be different if z ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when z is 3, the radical R ⁸ can be selected to form ethylene oxide (R ⁸ = H) or propylene oxide (R ⁸ = CH ₃ ) units which may be joined 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 z has been chosen here by way of example and may well be greater, with the variation range increasing with increasing z value and including, for example, a large number of EO groups combined with a small number of PO groups or vice versa.

Particularly preferred end-capped poly (oxyalkylated) alcohols of the formula (V) have values of k = 1 and j = 1, so that the formula (V) simplifies to formula (VI):

R ⁶ O [CH ₂ CH (R ⁸ )] _z CH ₂ CH (OH) CH ₂ OR ⁷ (VI).

In formula (VI) R ⁶ , R ⁷ and R ^{8 are} as defined in formula (V) and z is 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 ⁶ and R ^{7 have} 9 to 14 C atoms, R ^{8 is} hydrogen and z assumes values of 6 to 15.

Summarizing the last-mentioned statements, mixtures according to the invention are preferred which contain poly (oxyalkylated) compounds of the formula (V) which end-capped as nonionic surfactants, in which R ⁶ and R ^{7 are} linear or branched, saturated or unsaturated, aliphatic hydrocarbon radicals having 1 to 30 C atoms, R ^{8 is} hydrogen or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, z is values between 1 and 30, k and j are values from 1 to 12, preferably from 1 to 5, wherein surfactants of the formula (VI) in which z is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Very particular preference is given in the mixture according to the invention as component (b) to nonionic surfactants which are obtainable under the trade name Pluronic® from BASF AG.

The proportion of component (a) is 5 to 95 wt .-%, preferably 40 to 60 wt .-%. An exemplary proportion of component (a) is 50% by weight. Accordingly, component (b) is present in an amount of 5 to 95% by weight, preferably 40 to 60% by weight. An example is an amount of 50 wt .-%.

The mixed powders or mixed granules according to the invention can be prepared by mixing both components as a powder and then heating the mixture, in particular to a temperature above the melting or softening point of component (b). In this case, component (b) melts and intimately mixes with component (a). In the subsequent cooling and shaping process, the powder properties such as particle size and bulk density are adjusted.

The present invention also relates to a process for producing the mixed powders or mixed granules according to the invention by mixing the components (a) and (b) as a powder, heating the mixture and adjusting the powder properties in the subsequent cooling and shaping process.

Furthermore, it is possible to granulate the component (a) with the already melted component (b) and then to cool it.

With suitable mixing ratios (a) / (b), component (a) can also be stirred into the melt of component (b). The subsequent solidification and shaping takes place in accordance with the known processes of melt fabrication, for example by prilling or on cooling belts with, if necessary, downstream steps for adjusting the powder properties, such as grinding and sieving.

The mixed powders or mixed granules according to the invention can also be prepared by dissolving components (a) and (b) in a solvent and spray-drying the resulting mixture, wherein a granulation step can follow. In this case, the components (a) and (b) can be dissolved separately, wherein the solutions are subsequently mixed, or a powder mixture of the components can be dissolved in water. As solvents, it is possible to use all those which can dissolve components (a) and (b); preference is given, for example, to using alcohols and / or water, more preferably water.

The present invention thus also relates to a process for the preparation of the mixed powders or mixed granules according to the invention by dissolving components (a) and (b) in a solvent and spray-drying the resulting mixture, wherein a granulation step and / or a melt granulation step (see above) can follow.

The present invention also relates to the use of the mixed powders or mixed granules according to the invention for the production of solid detergents and cleaners, in the washing of textiles or in the cleaning of dishes. Both components unfold as mixed powder or mixed granules an effect in detergents and cleaning agents, for example as a dishwashing detergent for dishwashers.

The mixed powders or mixed granules can be incorporated into pulverulent detergents and cleaners without these clumping or caking.

The invention also relates to a solid detergent containing a mixed powder or mixed granules as described above and optionally at least one further surfactant. Suitable detergent compositions are known and, for example, in WO 95/29216 and EP-A-0 618 289 described.

The invention further relates to a solid dishwashing detergent containing a mixed powder or mixed granules, as described above, and also optionally at least one (further) surfactant. The agents are preferably present in powder or granular form.

Claims (12)

Mixed powder or mixed granules containing at least 80 wt .-% of a mixture of (a) 5 to 95% by weight of glutamic acid N, N-diacetic acid and / or one or more of its salts of general formula (I)

MOOC- (CH ₂ ) ₂ C (COOM) -N (CH ₂ COOM) ₂ (I)

with the meaning MH, NH ₄ , alkali metal, (B) 5 to 95 wt .-% of at least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof or a polymer selected from the group consisting of polyvinyl alcohols, polyvinylpyrrolidones (PVP), polyalkylene glycols and derivatives thereof. Mixed powder or mixed granules according to claim 1, characterized in that component (a) is an alkali metal salt of glutamic acid. Mixed powder or mixed granules according to claim 1 or 2, characterized in that the polyethylene glycol in component (b) has an average molecular weight (weight average molecular weight) of 500 to 30,000 g / mol. Mixed powder or mixed granules according to any one of claims 1 to 3, characterized in that the polyethylene glycol in component (b) OH and / or C _1-6 alkyl end groups. Mixed powder according to one of claims 1 to 4, characterized in that the nonionic surfactant in component (b) is selected from the group consisting of alkoxylated, primary alcohols, alkoxylated fatty alcohols, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides and polyhydroxy fatty acid amides. Mixed powder according to one of claims 1 to 5, characterized in that the nonionic surfactant in component (b) has a melting point of above 20 ° C. A process for the preparation of mixed powders or mixed granules according to any one of claims 1 to 6 by dissolving the components (a) and (b) in a solvent and spray-drying the resulting mixture, which may be followed by a granulation step. A process for producing mixed powders or mixed granules according to any one of claims 1 to 6 by mixing the components (a) and (b) as a powder, heating the mixture and adjusting the powder properties in the subsequent cooling and shaping process. Use of mixed powders or mixed granules according to one of claims 1 to 6 for the production of solid washing and cleaning agents, in the washing of textiles or in the cleaning of dishes. Solid detergent containing a mixed powder or mixed granules according to any one of claims 1 to 6 and optionally at least one (further) surfactant. A solid dishwashing detergent containing a mixed powder or mixed granules according to any one of claims 1 to 6 and optionally at least one further surfactant. Composition according to claim 10 or 11 in powder or granular form.