WO2013160132A1

WO2013160132A1 - Solid formulations, production thereof, and use thereof

Info

Publication number: WO2013160132A1
Application number: PCT/EP2013/057762
Authority: WO
Inventors: Stephan Hüffer; Alejandra Garcia Marcos; Markus Hartmann
Original assignee: Basf Se; Basf Schweiz Ag
Priority date: 2012-04-25
Filing date: 2013-04-15
Publication date: 2013-10-31

Abstract

The invention relates to the use of solid formulations with a residual moisture content ranging from 0.1 to 1 wt.%, containing (A) at least one compound, selected from aminocarboxylates and polyaminocarboxylates, and (B) at least one cationic (co)polymer with a cationic charge density of at least 5 mEq/g, (C) at least one silicate, selected from sodium silicates, potassium silicates, and aluminosilicates, (D) optionally at least one compound, selected from alkali metal percarbonate, alkali metal perborate, and alkali metal persulfate, and (E) optionally polyvinyl alcohol for the production of or as formulations for washing dishes and cooking utensils.

Description

Solid formulations, their preparation and use

The present invention relates to the use of solid formulations having a residual moisture content in the range of 0.1 to 15 wt .-%, containing

(A) at least one compound selected from aminocarboxylates and polyaminocarboxylates, and

(B) at least one cationic (co) polymer having a cationic charge density of at least 5 meq / g,

(C) at least one silicate selected from sodium silicates, potassium silicates and aluminosilicates, (D) optionally at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, and

(E) optionally polyvinyl alcohol,

as or for the preparation of formulations for washing dishes and kitchen utensils.

Furthermore, the present invention relates to solid formulations and to a process for the preparation of solid formulations according to the invention.

Modern dishwashing detergents have many requirements to fulfill. So they have to clean the dishes thoroughly, they should not leave any harmful or potentially harmful substances in the sewage, they should allow the draining and drying of the water from the dishes, and they should not cause problems when operating the dishwasher. Finally, they should not lead to aesthetically undesirable consequences on the good to be cleaned. Especially in this context is the glass corrosion.

Glass corrosion is caused not only by mechanical effects, for example, by juxtaposition of glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences. For example, certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.

Glass corrosion has several effects. On the one hand, one can observe the formation of microscopically fine cracks, which are noticeable in the form of lines. On the other hand, in many cases one can observe a general cloudiness, for example a roughening, which makes the glass in question look unaesthetic. Overall, such effects are also subdivided into iridescent discoloration, scoring and surface and annular opacities.

WO 2002/64719 discloses that it is possible to use certain copolymers of ethylenically unsaturated carboxylic acids with, for example, esters of ethylenically unsaturated carboxylic acids in dishwashing detergents. From WO 2010/020765 dishwashing agents are known which contain polyethyleneimine. Such dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion. Zinc and bismuth-containing dishwashing detergents are not recommended. However, glass corrosion, in particular line corrosion and turbidity, is in many cases not sufficiently delayed or prevented.

EP 2 392 638 discloses that aminocarboxylates may be used in admixture with silicates or with a second aminocarboxylate to produce the less hygroscopic automatic dishwashing formulations. However, glass corrosion can not be combated with sufficient efficiency in many cases.

It was therefore the object to provide formulations which are suitable for use as or for the production of dishwashing detergents and which avoid the disadvantages known from the prior art and inhibit or at least reduce the glass corrosion particularly well. A further object was to provide a process for the preparation of formulations which are suitable as or for the production of dishwasher detergents and which avoid the disadvantages known from the prior art. It was also the task to provide uses of formulations. Accordingly, the formulations defined above were found, also referred to as formulations according to the invention, and the corresponding use as or for the preparation of formulations for the automatic rinsing of dishes and kitchen utensils.

Formulations used according to the invention have a residual moisture in the range from 0.1 to 15% by weight, preferably at least 2 to 10% by weight, particularly preferably 4 to 7% by weight. The residual moisture is based on the total formulation used according to the invention. The residual moisture can preferably be determined gravimetrically, for example by drying the formulation according to the invention at 120 ° C. to constant weight. Contain formulations used according to the invention

(A) at least one compound selected from aminocarboxylates and polyaminocarboxylates, in the context of the present invention also briefly aminocarboxylate (A) or Polyaminocar- boxylate (A) or compound (A) mentioned, and preferably their salts. Compound (A) may be in the form of a free acid or preferably in partially or completely neutralized form, ie as a salt. As counterions, for example inorganic cations, such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg ^2+, Ca ^2+, Na ^+, K ^+, or organic cations, preferably with one or more organic radicals, substituted ammonium, more particularly triethanolammonium, Ν, Ν-diethanolammonium, N-mono-C 1 -C 4 -alkyldiethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N, N-di-C 1 -C 4 -alkylethanolammonium. In the context of the present invention, aminocarboxylates (A) are understood to mean nitrilotriacetic acid and those organic compounds which have a tertiary amino group which has one or two Ch-COOH groups which, as mentioned above, can be partially or completely neutralized or . can. In the context of the present invention, polyaminocarboxylates (A) are understood as meaning those organic compounds which have at least two tertiary amino groups which independently of one another have one or two Ch-COOH groups which, as mentioned above, can be partially or completely neutralized or . can. In another embodiment of the present invention, aminocarboxylates (A) are selected from those organic compounds having a secondary amino group having one or two CH (COOH) CH 2 -COOH group (s) partially or partially substituted as mentioned above can be completely neutralized or can. In another embodiment of the present invention, polyaminocarboxylates (A) are selected from those organic compounds which have at least two secondary amino groups, each containing a CH (COOH) CH 2 COOH group, which, as mentioned above, partially or completely can be neutralized.

Preferred polyaminocarboxylates (A) are selected from 1,2-diaminoethanetetraacetic acid (EDTA), diethylenetriamine pentaacetate (DTPA), hydroxyethylenediaminetriacetate (HEDTA), and their respective salts, more preferably alkali metal salts, in particular the sodium salts.

Preferred aminocarboxylates (A) and polyaminocarboxylates (A) are nitrilotriacetic acid and those organic compounds having an amino acid-based structure whose amino group (s) have one or two CH 2 -COOH groups and are tertiary amino groups. It is possible to select amino acids from L-amino acids, R-amino acids and mixtures of enantiomers of amino acids, for example the racemates.

In one embodiment of the present invention, compound (A) is selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA), and preferably from their salts, in particular the sodium salts of MGDA, IDS and GLDA. Very particular preference is given to methylglycine diacetate and to the trisodium salt of MGDA.

The formulation used according to the invention also contains

(B) at least one cationic (co) polymer having a cationic charge density of at least 5 milliequivalents / g, also called cationic (co) polymer (B). Preferred (co) polymers (B) are selected from polyvinylamine and linear and branched homopolymers of alkyleneimine. Particularly preferred (co) polymers (B) are selected from homopolymers and copolymers of ethyleneimine, also known as polyethylenimine (B), and homopolymers and copolymers of propylenimine, in short also called polypropyleneimine (B). Cationic (co) polymers (B) in the context of the present invention are understood to mean those (co) polymers which have at least one of the following structural features:

(i) permanent cationic charges, for example quaternary nitrogen atoms, for example in the form of trialkylammonium groups, 3-alkylimidazolium groups,

Arylimidazolium groups, tetra (2-aminoethyl) groups, tetra (2-iminoethyl) groups, N-pyridinium groups, or Ν, Ν-dialkylimino groups, preferred are tri-C 1 -C 4-n-alkylammonium groups, 3-methylimidazolium groups, 3-phenylimidazolium groups and tetra (2-aminoethyl) groups, or

(ii) basic nitrogen atoms which are protonated at a pH of, for example, 5 or less, preferably 1 to 3, in an aqueous medium. Examples are -NH ₂ groups, - NH (Ci-Cio-alkyl) groups, -N (Ci-Cio-alkyl) ₂ groups, -NH (C ₂ -Cio-alkylene) groups, - (CH ₂ ) 2-N (CH ₃ ) 2 groups, NH-CH ₂ CH (Ci-Cio-alkyl) groups and - (C ₂ -Cio-alkylene) N (C ₂ - Cio-alkylene) groups, especially CH ₂ -CH ₂ -NH-CH ₂ -CH ₂ -NH- groups and CH ₂ -CH ₂ - NH- (CH ₂ ) ₃ -NH- groups.

Cationic (co) polymer (B) may have at least two structural features (i) per molecule, which may be the same or different, or at least two structural features

(ii), which may be the same or different, or at least one structural feature (i) and at least one structural feature (ii). Preferably, cationic (co) polymer per molecule

(B) at least five structural features (i), which may be the same or different, or at least five structural features (ii), which may be the same or different.

Cationic (co) polymer (B) can have as counter ions high molecular weight or low molecular weight anions, organic or preferably inorganic. High molecular weight anions in the context of the present invention have an average molecular weight of 200 g / mol or more, for example up to 2500 g / mol, low molecular weight anions have a molecular weight of less than 200 g / mol, for example from 17 to 150 g / mol. Examples of low molecular weight organic counterions are acetate, propionate and benzoate. Examples of low molecular weight inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate and bicarbonate.

Cationic (co) polymers (B) have a cationic charge density of at least 5 milliequivalents / g, with the statement in g referring to cationic (co) polymer (B) without consideration of the counterions. A charge density in the range of 5 to 22 milliequivalents / g is preferred. The cationic charge density can be determined, for example, by titration.

Cationic (co) polymers (B) may also contain one or more anionic comonomers copolymerized, for example (meth) acrylic acid. Cationic copolymers (B), which also contain one or more anionic comonomers polymerized, have more cationic than anionic charges per molecule. In another embodiment of the present invention, cationic (co) polymer (B) contains no anionic comonomers in copolymerized form.

Examples of cationic (co) polymers (B) are polyvinylamine-co-vinylformamide, which can be prepared, for example, by partial hydrolysis of polyvinylformamide, furthermore polyvinylpyrrolidone, PolyDADMAC (DADMAC: diallyldimethylammonium chloride), polyvinylpyrrolidone-co-vinyl-3-methylimidazolium, graft copolymers of 3-methyl -N-vinylimidazolium on polyethers such as polyethylene glycol or polypropylene glycol, graft copolymers of 3-methyl-N-vinylimidazolium and N-vinylpyrrolidone on polyethers such as polyethylene glycol or polypropylene glycol.

Further examples of cationic (co) polymers (B) are copolymers of (meth) acrylates with N, N-dimethylaminoethyl (meth) acrylate and copolymers of (meth) acrylates with Ν, Ν, Ν-trimethylammoniumethyl (meth) acrylate. Another example is cationically modified starch.

According to a particular embodiment of the invention, cationic (co) polymer (B) has an average molecular weight M _{n of} from 500 g / mol to 125,000 g / mol, preferably from 750 g / mol to 100,000 g / mol.

In one embodiment of the present invention, cationic (co) polymer (B) has an average molecular weight M _w in the range of 500 to 1,000,000 g / mol, preferably in the range of 600 to 75,000 g / mol, particularly preferably in the range of 800 to 25,000 g / mol, determinable for example by gel permeation chromatography (GPC). Preferred (co) polymers (B) are selected from polyvinylamines, also referred to as polyvinylamines (B) for short, and from linear and branched homopolymers of alkyleneimines, in short polyalkylenimine (B), and in particular from linear and branched homopolymers of ethyleneimine and / or propyleneimine, polyethylenimine (B) or polypropyleneimine (B) for short.

Examples of polyvinylamines (B) are not only fully saponified polyvinylamides, for example fully saponified poly-N-vinylformamide, but also so-called hydrophobically modified polyvinylamines, for example by reaction with - one or more linear carboxylic acids with 10 to 22 carbon atoms / molecule, preferably with 14 to 18 carbon atoms / molecule, for example capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, nonadaptanic acid, linoleic acid, oleic acid, palmitoleic acid, arachidonic acid, behenic acid, stearic acid, oleic acid and Palmitic acid or its esters, in particular ethyl or methyl esters, their acid chlorides or their anhydrides, one or more linear or branched alkyl halide (s) having from 10 to 22 carbon atoms / molecule, preferably from 14 to 18 carbon atoms / molecule, for example n-tetradecyl chloride, n-hexadecyl chloride, n-octadecyl chloride,

one or more alkyl epoxides having 10 to 22 carbon atoms / molecule, for example 1, 2-hexadecenyl oxide and 1, 2-octadecenyloxide,

Alkyl ketene dimers having 9 to 21 carbon atoms in the respective alkyl radical, preferably up to 18 carbon atoms, for example dimeric lauryl ketene, dimeric palmityl ketene, lower stearyl ketene and dimeric oleyl ketene, or mixtures thereof,

cyclic dicarboxylic acid anhydrides, in particular alkyl-substituted succinic anhydrides having 10 to 22 carbon atoms in the alkyl radical, preferably 14 to 18 carbon atoms in the alkyl radical, for example dodecenylsuccinic anhydride, tetradecylsuccinic anhydride, hexadecenylsuccinic anhydride, and mixtures thereof, chloroformates of fatty alcohols having 10 to 22 carbon atoms in the alkyl radical, preferably with 14 to 18 carbon atoms in the alkyl radical,

- Alkylene diisocyanates having 10 to 22 carbon atoms in the alkylene radical, preferably having 14 to 18 carbon atoms in the alkyl radical, for example OCN- (CH ₂ ) i4-NCO, OCN- (CH ₂ ) i6-NCO or OCN- (CH ₂ ) i8-NCO or mixtures at least two of the aforementioned compounds. Polyalkyleneimines (B) in the context of the present invention can be prepared not only by polymerization of alkyleneimine, but also, for example, by polycondensation of a ^ -hydroxy-C2-Cio-Alkylenaminen, by polycondensation of a, (jo-C2-Cio-alkylenediamines with a, (jo-hydroxy-C 2 -C 10 -alkylenediols or by polycondensation of α, oo-C 2 -C 10 -alkylenediamines An example of the polycondensation of α 1 -C -hydroxy-C 2 -C 10 -alkyleneamines is the polycondensation of triethanolamine.

In one embodiment of the present invention, polyethyleneimine (B) has an average molecular weight M _w in the range of 600 to 75,000 g / mol, preferably in the range of 800 to 25,000 g / mol.

In one embodiment of the present invention, polyethyleneimines (B) are selected from highly branched polyethyleneimines (B). Highly branched polyethylenimines (B) are characterized by their high degree of branching (DB). The degree of branching can be determined, for example, by ¹³ C-NMR spectroscopy, preferably in D 2 O, and is defined as follows:

DB = D + T / D + T + L with D (dendritic) corresponding to the proportion of tertiary amino groups, L (linear) corresponding to the fraction of secondary amino groups and T (terminal) corresponding to the proportion of primary amino groups. In the context of the present invention, highly branched polyethyleneimines (B) are polyethyleneimines (B) with DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90, more preferably in the range from 0.30 to 0.80 and most preferably at least 0.5. In the context of the present invention, polyethylene dendrimers (B) which are dendrimeric polyethylenimines (B) are those which have a structurally and molecularly uniform structure.

In one embodiment of the present invention, polyethylenimine (B) is highly branched polyethyleneimines (homopolymers) having an average molecular weight M _w in the range from 600 to 75,000 g / mol, preferably in the range from 800 to 25,000 g / mol.

According to a particular embodiment of the invention, polyethylenimine (B) is highly branched polyethyleneimines (homopolymers) having an average molecular weight M _{n of} from 500 g / mol to 125,000 g / mol, preferably from 750 g / mol to 100,000 g / mol be selected from dendrimers.

In one embodiment of the present invention, polyethylenimine (B) is a polyethylenimine modified with carboxylate groups or alkoxylate groups, in particular a polyethylenimine modified with ethoxylate, propoxylate or acetate by Michael addition of acrylic acid.

Formulations used according to the invention comprise at least one silicate, also called silicate (C) for short, selected from sodium silicates, potassium silicates and aluminosilicates. Examples are in particular sodium disilicate and sodium metasilicate, aluminosilicates (zeolites) and

Phyllosilicates.

In one embodiment of the present invention is selected silicate (C) from those of nominal composition M ₂ 0 ^■ x Si0 ₂ wherein M is selected from potassium, sodium or mixtures of potassium and preferably sodium and x is in the range of 1 to 3.5, preferably in the range of 1.6 to 2.6, and more preferably in the range of 1.8 to 2.2. Particular preference is given to silicates of the formula a-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ , and 5-Na ₂ Si ₂ O ₅ .

In one embodiment of the present invention, silicate (C) is selected from hydrous silicates wherein water may be physisorbed or chemically bound.

In one embodiment of the present invention, silicate (C) has a zero zeta potential. In one embodiment of the present invention, silicate (C) in combination with cationic (co) polymer (B) has a zero zeta potential. In one embodiment of the present invention, silicate (C) has an average primary particle diameter in the range of 10 to 1000 nm, preferably 50 to 500 nm, determinable, for example, by image analysis by electron microscopy.

In one embodiment of the present invention, silicate (C) in the formulation according to the invention is composed of agglomerates of silicate primary particles. The agglomerates mentioned may have a mean diameter (number average) in the range of 0.5 to 100 μm, preferably 1 to 20 μm (determinable, for example, by electron microscopy or by Coulter Counter).

Formulations used according to the invention may further contain:

(D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, in the context of the present invention also called "bleaching agent (D)".

Preferred bleaching agents (D) are selected from sodium perborate, anhydrous or, for example, as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, and sodium persulfate, where the term "persulfate" in each case the salt of peracid H2SO5 and the peroxodisulfate with includes.

The alkali metal salts may each also be alkali metal hydrogencarbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulphate. However, preference is given in each case to the dialkali metal salts. In one embodiment of the present invention, formulation according to the invention comprises polyvinyl alcohol (E), wherein polyvinyl alcohol in the context of the present invention comprises completely and substantially, for example at least 95 mol%, preferably at least 96 mol% hydrolyzed polyvinyl acetate. In one embodiment of the present invention, the formulation according to the invention may comprise polyvinyl alcohol (E), for example 0.5 to 5% by weight, based on the solids content of the formulation used according to the invention.

In one embodiment of the present invention, polyvinyl alcohol (E) has an average molecular weight M _n in the range of 22,500 to 15,000 g / mol, for example up to 40,000 g / mol. In one embodiment of the present invention, polyvinyl alcohol (E) has an average molecular weight M _w in the range from 2,000 to 40,000 g / mol.

In one embodiment of the present invention, formulations used according to the invention contain formulations

total in the range of 1 to 50% by weight of compound (A), preferably 10 to 25% by weight, in total 0.001 to 2% by weight of cationic (co) polymer (B), preferably 0.02 to 0.5 Wt .-%, in the range of 1 to 30 wt .-% silicate (C) and in total zero to 15% by weight of bleaching agent (D) selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate,

total in the range of zero to 5% by weight polyvinyl alcohol (E),

in each case based on solids content of the relevant formulation.

In a variant of the present invention formulation according to the invention contains compound (A) and cationic (co) polymer (B) in a weight ratio of 1000: 1 to 25: 1. In one embodiment of the present invention, formulation according to the invention is solid at room temperature, for example a powder or a tablet. In another embodiment of the present invention, formulation of the invention is liquid at room temperature. In one embodiment of the present invention, the formulation according to the invention is a granulate, a liquid formulation or a gel.

In one embodiment of the present invention, formulation according to the invention is free of phosphates and polyphosphates, wherein hydrogen phosphates are subsumed, for example, free of trisodium phosphate, pentasodium tripolyphosphate and Hexasatriummeta- phosphate. The term "free of" in connection with phosphates and polyphosphates in the context of the present invention is understood to mean that the total content of phosphate and polyphosphate is in the range from 10 ppm to 0.2% by weight, determined by gravimetry.

In one embodiment of the present invention, the formulation according to the invention is free from those heavy metal compounds which do not function as bleach catalysts, in particular compounds of iron and bismuth. In the context of the present invention, "free from" is to be understood in connection with heavy metal compounds as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in the range from 0 to 100 ppm, determined by the Leach method and based on The formulation according to the invention preferably has a heavy metal content below 0.05 ppm.

For the purposes of the present invention, "heavy metals" are all metals having a specific density of at least 6 g / cm ^3. In particular, heavy metals are noble metals and also zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.

Preferably, formulation of the invention contains no measurable levels of zinc and bismuth compounds, that is, for example, less than 1 ppm.

In one embodiment of the present invention, the formulation used according to the invention may comprise further ingredients (F), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more co-builders, sodium citrate, one or more several alkali carriers, one or more Bleach, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more perfumes, one or more organic solvents, one or more Tableting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizing agents.

Examples of surfactants are, in particular, nonionic surfactants and mixtures of anionic or zwitterionic surfactants with nonionic surfactants. Preferred nonionic surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I)

where the variables are defined as follows:

R ^{1 is} identical or different and selected from linear C ¹ -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,

R ² selected from Cs-C22-alkyl, for example nC & Hn, n-doFi, n-Ci2H25, nC-uF s), n-Ci6H33

R ^{3 is} selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. -Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or iso-decyl, m and n are in the range of zero to 300, the sum of n and m being at least one. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.

Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II)

in which the variables are defined as follows: R ^{1 is} identical or different and selected from linear C ¹ -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,

R ^{4 is} selected from C 6 -C 20 -alkyl, in particular n-CsH-i, n-doH-i, n-C 12 H 25, nC-uF s), n-C 16 H 33, n

a is a number in the range of 1 to 6, b is a number in the range of 4 to 20, d is a number in the range of 4 to 25.

In the case of compounds of the general formula (II), these may be block copolymers or random copolymers, preference being given to block copolymers.

Other suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Also suitable are amine oxides or alkyl glycosides. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187.

It may also contain mixtures of several different nonionic surfactants.

Examples of anionic surfactants are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates having one to six ethylene oxide units per molecule.

In one embodiment of the present invention, the formulation used according to the invention may contain in the range of from 3 to 20% by weight of surfactant.

Formulations used in the invention may contain one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.

For example, formulations used according to the invention may contain up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, based in each case on the total solids content of the formulation according to the invention. Formulations used according to the invention may comprise, in addition to sodium citrate, one or more builders, in particular phosphate-free builders. Examples of suitable builders are citric acid and its alkali metal salts, in particular sodium citrate, fatty acid sulfonates, α-hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example polycarboxylates and polyaspartic acid , Particularly preferred is sodium citrate. In one embodiment of the present invention, builders of polycarboxylates, for example, alkali metal salts of (meth) acrylic acid homo- or

(Meth) acrylic acid copolymers.

Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M _w in the range from 2000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.

It is also possible copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C3-Cio-mono- or C4-Cio-dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid with at least one hydrophilic or hydrophobically modified monomers as enumerated below.

Examples of suitable hydrophobic monomers are isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof such as, for example, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docoses, 1-tetracoses and 1 -hexacoses, C22-α-olefin, a mixture of C2o-C24-α-olefins and polyisobutene having an average of 12 to 100 carbon atoms per molecule.

Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples which may be mentioned are: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate. Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule. Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2 hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and salts of said acids, such as their sodium, potassium or ammonium salts. Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.

In addition, amphoteric polymers can also be used as builders. Formulations used according to the invention may contain, for example, in the range from 10 to 50% by weight, preferably up to 20% by weight, of builder.

In one embodiment of the present invention, formulations used according to the invention may contain one or more co-builders.

Examples of cobuilders are phosphonates, for example hydroxyalkanephosphonates and aminoalkanephosphonates. Among the hydroxyalkane phosphonates, the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.

Formulations of the invention may contain sodium citrate. The term sodium citrate includes the mono-, the disodium salt, but most preferably designates the trisodium salt. Sodium citrate can be used as anhydrous salt or as a hydrate, for example as a dihydrate.

Formulations used according to the invention may contain one or more alkali carriers. Alkaline carriers, for example, provide the pH of at least 9 when an alkaline pH is desired. Examples of suitable compounds are alkali metal carbonates, alkali metal hydroxycarbonates, alkali metal hydroxides and alkali metal metasilicates. Preferred alkali metal is in each case potassium, particularly preferred is sodium. Formulations used according to the invention may contain, in addition to bleaching agent (D), one or more chlorine-containing bleaching agents.

Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

Formulations used according to the invention may contain, for example, in the range of from 3 to 10% by weight of chlorine-containing bleach.

Formulations used in the invention may contain one or more bleach catalysts. Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or carbonyl complexes. Also, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod

Ligands as well as cobalt, iron, copper and ruthenium amine complexes are useful as bleach catalysts.

Formulations used according to the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts"), trimethylammonium-maucetonitrile salts, N-acylimides such as N-nonanoylsuccinimide "1, 5-diacetyl-2,2- dioxo-hexahydro-1, 3,5-triazine ("DADHT") or nitrile quats (trimethylammonium acetonitrile salts). Other examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

Formulations used in the invention may contain one or more corrosion inhibitors. This is to be understood in the present case, such compounds that inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol. In one embodiment of the present invention, formulations used in the invention contain a total of in the range of 0.1 to 1, 5 wt .-% corrosion inhibitor.

Formulations used in the invention may contain one or more builders, for example, sodium sulfate.

Formulations used according to the invention may contain one or more defoamers selected, for example, from silicone oils and paraffin oils. In one embodiment of the present invention, formulations used according to the invention generally contain in the range from 0.05 to 0.5% by weight defoamer.

Formulations used according to the invention may contain phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1, 1-diphosphonic acid.

According to the invention, the above-described formulations are used for machine cleaning of dishes and kitchen utensils. For the purposes of the present invention, kitchen utensils include, for example, pots, pans and casseroles, furthermore metal objects such as, for example, skimmers, roasting knives and garlic presses.

Preference is given to the use of formulations according to the invention for machine cleaning of articles which have at least one surface made of ceramic or preferably glass, which may be decorated or not decorated. In the context of the present invention, a surface of glass is to be understood as meaning that the object in question has at least one piece of glass which comes into contact with the ambient air and can be contaminated when the object is used. Thus, the objects in question may be those which are essentially glassware such as drinking glasses or glass bowls. But it can also be, for example, cover that have individual components of a different material, such as pot lid with edging and handle made of metal or ceramic.

Ceramic or preferably glass surface may be decorated, for example colored or printed, or not decorated.

The term "glass" includes any glass, for example lead glass and in particular soda lime glass, crystal glass and borosilicate glasses.

Mechanical cleaning preferably involves rinsing with a dishwashing machine (English: automatic dishwashing).

In one embodiment of the present invention, at least one formulation according to the invention is used for the automated cleaning of drinking glasses, glass vases and glass vessels for cooking.

In one embodiment of the present invention, water having a hardness in the range from 1 to 30 ° dH, preferably from 2 to 25 ° dH, is used for cleaning, German hardness being taken to mean in particular the calcium hardness. If one uses formulations according to the invention for machine cleaning, it is observed even with repeated mechanical cleaning of objects that have at least one surface of glass, only very low tendency for glass corrosion, and even when you clean objects that have at least one glass surface together with heavily soiled cutlery or dishes. In addition, it is much less harmful to use the formulation according to the invention to clean glass together with metal objects, for example together with pots, pans or garlic presses.

Another object of the present invention are formulations having a residual moisture content of 0.1 to 15 wt .-%, preferably up to 10 wt .-%, containing

(C) at least one silicate selected from sodium silicates, potassium silicates and aluminosilicates,

(D) optionally at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, and

(E) optionally polyvinyl alcohol.

Compound (A), cationic (co) polymer (B), silicate (C) and bleach (D), and polyvinyl alcohol (E) are described above.

In one embodiment of the present invention, formulation of the invention is free of phosphates and polyphosphates. The term "free of" in the context of phosphates and polyphosphates is defined above In one embodiment of the present invention, cationic (co) polymer (B) is selected from polyvinylamine and linear and branched homopolymers of alkyleneimine, especially from linear and branched homopolymers of ethyleneimine and / or propylene imine.

In one embodiment of the present invention, the formulation according to the invention has a heavy metal content in the range from 0 to 100 ppm, preferably below 0.05 ppm, based on the solids content of the relevant formulation.

In one embodiment of the present invention, formulation according to the invention may comprise polyvinyl alcohol, for example 0.5 to 5% by weight, based in each case on the solids content of the relevant formulation according to the invention.

In one embodiment of the present invention, compound (A) is selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, in particular the sodium salts.

In one embodiment of the present invention, formulation according to the invention contains: in total in the range from 1 to 50% by weight of compound (A),

in the range of 0.001 to 2% by weight of cationic (co) polymer (B), in the range of 1 to 30 wt .-% silicate (C) and

Total in the range of zero to 15% by weight of bleach (D)

total in the range of zero to 5% by weight polyvinyl alcohol (E),

in each case based on solids content of the relevant formulation.

In one embodiment of the present invention, silicate (C) in the formulation according to the invention has a mean primary particle diameter (number average) in the range from 10 to 1, 000 nm, preferably 50 to 500 nm, determinable, for example, by image analysis with the aid of electron microscopy.

In one embodiment of the present invention, silicate (C) in the formulation according to the invention is composed of agglomerates of silicate primary particles. The agglomerates mentioned may have an average diameter in the range of 0.5 to 100 μm, preferably 1 to 20 μm (number average, image analysis with the aid of electron microscopy).

Another object of the present invention is a process for the preparation of formulations according to the invention. For the preparation of formulations according to the invention, it is possible to proceed in such a way that

(A) at least one compound selected from aminocarboxylates and polyaminocarboxylates,

(C) at least one silicate or water glass,

(E) optionally polyvinyl alcohol (E)

mixed in one or more steps with each other in the presence of water and then partially removed the water. Preferably, the procedure is to remove water by compaction or preferably by spray drying or spray granulation.

If it is desired to prepare formulations which contain bleaches (D) and / or polyvinyl alcohol (E) and / or at least one additional component (F) (ingredient (F)), it is possible first to prepare a formulation according to the invention which comprises compound (A), cationic (co) polymer (B), silicate (C) and optionally polyvinyl alcohol (E), and mixing them with bleach (D) and / or one or more additional components (F), dry or in the presence of water. In another variant, one can proceed by preparing an aqueous formulation containing more than 15 wt .-% water, based on the sum of all solids in the formulation in question, and the compound (A), cationic (co) polymer (B), silicate (C), optionally polyvinyl alcohol (E) and at least one further component selected from bleach (D) and at least one additional component (F). Thereafter, the water is partially removed, so that a formulation according to the invention having a residual moisture of 0.1 to 15 wt .-%.

In another variant, one can proceed by first treating a silicate (C) with at least one cationic (co) polymer (B) and then - preferably in the presence of water - with compound (A) and polyvinyl alcohol (E). Then you can partially remove the water. Thereafter, it is possible to mix with bleach (D) and / or one or more additional components (F), preferably in the presence of water, and then at least partially remove the water.

In another variant, one can proceed by preparing an aqueous formulation containing more than 15 wt .-% water, based on the sum of all solids in the formulation in question, and the compound (A), cationic (co) polymer (B), water glass, optionally polyvinyl alcohol (E) and at least one further component selected from bleach (D) and at least one additional component (F). Thereafter, the water is partially removed, so that a formulation according to the invention having a residual moisture of 0.1 to 15 wt .-%. Silicate (C) is formed in s fu.

In a preferred embodiment of the present invention, the water is partially removed, that is, to a residual moisture content of the relevant formulation of the invention in the range of 0.1 to 15 wt .-%, preferably 2 to 10 wt .-%, particularly preferably 4 to 7 wt %, by spray drying or spray granulation, using one or more spray towers and operating at a gas inlet temperature in the range of 120 to 220 ° C.

If it is desired to remove water by spray-drying, it is preferable to add polyvinyl alcohol (E), for example from 0.5 to 5% by weight, based on the solids content of the formulation in question.

In one embodiment of the present invention, the water is removed by freeze-drying. The invention will be further explained by working examples. General remarks:

The charge density of cationic (co) polymers (B) was always determined as follows (see also: Horn, Prog. Colloid & Polym., Sci. 1978, 65, 251):

1 g of the relevant (co) polymer was dissolved in 100 ml of demineralized water. With a buffer solution and aqueous HCl was set to a pH of 4.0, determined potentiometrically. Three ml of an aqueous solution of toluidine blue (50 mg / l water) was added and titrated N / 400 KPVS (potassium polyvinyl sulfate) solution (Wako Co.) at a concentration of 0.0004 meq / ml to a color change from blue to pink. They charged the charge density as follows: LA = 0.4 ^■ KV with

LA: charge density of the relevant (co) polymer (B), meq / g (milliequivalent / g) KV: consumption of N / 400-KPVS solution [ml]

I. Preparation of formulations according to the invention

1.1 Preparation of basic mixtures

First, base mixtures were prepared from the starting materials according to Table 1. The starting materials were dry-mixed except for the sodium silicate, which was metered separately as a 30% by weight solution.

Table 1: Basic mixtures for experiments with formulations according to the invention and comparative formulations

All information in g.

Abbreviations:

MGDA: methylglycine diacetic acid as trisodium salt

TAED: Ν, Ν, Ν ', Ν'-tetraacetylethylenediamine

HEDP: disodium salt of hydroxyethane- (1, 1-diphosphonic acid)

I.2 Preparation of formulations according to the invention

1.2.1 Preparation of the formulations 2 to 13 according to the invention and of the comparative formulations V1 to V8

The following cationic (co) polymers were used:

(B.1): polyethyleneimine homopolymer, M _w 800 g / mol, DB 0.63, charge density of 19 meq / g (B.2): Polyethyleneimine homopolymer, M _w 2,000 g / mol, DB 0.64, Charge density 18 meq / g (B.3): Polyethyleneimine homopolymer, M _w 5,000 g / mol, DB 0.67, Charge density 17 meq / g (B.4): polyvinylamine, M _w 10,000 g / mol, charge density 20 meq / g

(B.5): Polyethyleneimine, ethoxylated, M _w 2800 g / mol, 1, 0 EO / NH, charge density 8 meq / g

(B.6): polyethyleneimine, propoxylated, M _w 3100 g / mol, 1.0 PO / NH, charge density 6 meq / g (B.7): polyethyleneimine, 20 mol% of the primary amino groups amidated with valeric acid, M _w 5300 g / mol, charge density 10 meq / g

(B.8): polyethyleneimine, carboxymethylated, sodium salt, carboxymethylation 30 mol% of the primary amino groups, M _w 6,000 g / mol, charge density 1 1 meq / g

(B.9): PolyTEA (polycondensate of triethanolamine) condensate, M _w 3000 g / mol, charge density 5 meq / g

Action:

20 ml of distilled water were placed in a 100 ml beaker and the cationic (co) polymer according to Table 2 was added with stirring.

Then it was stirred for 10 minutes. Then, MGDA trisodium salt (A.1) dissolved in 30 ml of water was added as shown in Table 2. A clear solution was obtained. The approximately 30% strength sodium disilicate solutions were then metered in according to the quantity indicated in Table 2 (above 100%). Thereafter, base mixture according to Table 2 was added, stirred again and evaporated the water.

(C.1): Na ₂ Si ₂ O ₅ , manufacturer PQ Corporation, 30% by weight in water

(C.2): Na ₂ Si ₂ O ₅ , manufacturer BASF SE, 32 wt .-% in water.

I.2.2: Preparation of Formulations 14 to 18 According to the Invention

First, a spray solution was prepared by stirring 15 parts by weight (A.1) in 30 parts by weight of water. Cationic polymer (B) according to Table 2 and then sodium disilicate solution (quantity see Table 2) were added. The spray solution thus obtained was spray-dried (temperature of the feed air stream: 150 ° C.) and then compacted. The resulting spray granules were mixed with the base mixtures according to Table 1 in a ratio.

There were obtained formulations according to the invention, which were tested according to Table 2.

The preparation of comparative formulations was carried out analogously, but left cationic

Polymer (B) or silicate (C) gone. By dosing in the test the corresponding proportions of base mixture separately from aqueous solution of (A.1), (B), (C.1) or (D.1), the same results were obtained as when one tested the dried formulation with equal amounts of active ingredients. So it does not depend on the order of the dosage.

If additionally 2.5% by weight of polyvinyl alcohol were used in the compaction, formulations with improved powder morphology (particle size, bulk density) and a reduced water absorption in the air were obtained.

II. Use of formulations according to the invention and comparative formulations for machine cleaning of glasses

General: Care was taken that after the first cleaning of the specimens in the household dishwasher until after weighing and visual patterning of the glasses, the specimens were only touched with clean cotton gloves, so that the weight or the visual impression of the specimens was not falsified.

The testing of formulations according to the invention and comparative formulations was carried out as follows.

11.1 Test method Dishwasher with endurance runner

Dishwasher: Miele G 1222 SCL

Program: 65 ° C (with pre-rinse)

Washware: 3 champagne glasses "GILDE", 3 shot glasses, "INTERMEZZO" For cleaning, the glasses were placed in the upper dish rack of the dishwasher. The dishwashing agent used was in each case 25 g of formulation according to the invention or 25 g of comparison formulation according to Table 2, where Table 2 shows the active components (A.1), base mixture, silicate (C.1 or C.2) and compound (D) or ( E) and (B) of inventive formulation individually specified. Rinsing was carried out at a rinse temperature of 55 ° C. The water hardness was in each case in the range of zero to 2 ° dH. One rinsed 100 each

Rinse cycles, i.e., the program was run 100 times. The evaluation was carried out gravimetrically and visually after 100 rinsing cycles.

The weight of the glasses was determined before the beginning of the first rinse cycle and after drying after the last rinse cycle. The weight loss is the difference between the two values.

In addition to the gravimetric evaluation, a visual evaluation of the items to be cleaned was carried out after 100 cycles in a darkened chamber under light behind a pinhole. One used a grading scale from 1 (very bad) to 5 (very good). In each case grades for area corrosion / turbidity or line corrosion were determined.

Experimental procedure: First, they rinsed for the purpose of pretreatment, the test pieces in a domestic dishwashing machine (Bosch SGS5602) with 1 g of surfactant (n-Ci8H37 (OCH ₂ CH 2) ioOH) and 20 g of citric acid, to remove any impurities. The test pieces were dried, their weight determined and fixed on the grid floor insert.

To assess the gravimetric removal, the dry specimens were weighed. This was followed by the visual assessment of the test specimens. The surface of the test specimens was evaluated for line corrosion (glass scoring) and haze corrosion (areal haze).

The assessments were made according to the following scheme.

Line corrosion:

L5: no lines to recognize

L4: in very few areas low line formation, fine line corrosion

L3: line corrosion in some areas

L2: line corrosion in several areas

L1: Strong line corrosion

glass opacity

L5: no haze visible

L4: low turbidity in very few areas

L3: cloudiness in some areas

L2: cloudiness in several areas

L1: markedly turbid over almost the entire glass surface

Interim scores (e.g., L3-4) were also allowed on the match. If hardness water at 2 ° dH was used instead of water for the tests, formulations according to the invention were also always superior to the corresponding comparative formulations in terms of the inhibition of glass corrosion.

II.3 Results

The results are summarized in Table 2. Table 2: Results of tests with dishwasher (endurance runner)

Table 2 (continued)

Claims

claims

Use of solid formulations having a residual moisture content in the range of 0.1 to 15 wt .-%, containing

(E) optionally polyvinyl alcohol

2. Use according to claim 1, characterized in that the formulation is free of phosphates and polyphosphates.

Use according to claim 1 or 2, characterized in that cationic (co) polymer (B) is selected from polyvinylamine and linear and branched homopolymers of alkyleneimine.

Use according to one of claims 1 to 3, characterized in that the formulation has a heavy metal content below 0.05 ppm, based on the solids content of the formulation in question.

Use according to any one of claims 1 to 4, characterized in that compound (A) is selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate and their salts.

Use according to one of claims 1 to 5, characterized in that silicate (C) has an average primary particle diameter of at most 1 μηη.

Use according to any one of claims 1 to 6, characterized in that the formulation contains:

in total in the range from 1 to 50% by weight of compound (A),

in the range of 0.001 to 2% by weight of cationic (co) polymer (B),

in the range from 1 to 30% by weight of silicate (C)

in total in the range of zero to 15% by weight of bleach (D) and

total in the range of zero to 5% by weight polyvinyl alcohol (E),

in each case based on solids content of the relevant formulation.

8. Use according to one of claims 1 to 7, characterized in that one selects dishes and kitchen utensils from those having at least one surface of glass or ceramic, which may be decorated or not decorated.

9. Use according to one of claims 1 to 8, characterized in that the rinsing is a rinsing with a dishwasher.

10. Solid formulations having a residual moisture content in the range of 0.1 to 15 wt .-%, containing

(C) at least one silicate selected from sodium silicates, potassium silicates and alumino-silicates,

(E) optionally polyvinyl alcohol.

1 1. Formulation according to claim 10, characterized in that it is free of phosphates and polyphosphates.

12. A formulation according to claim 10 or 1 1, characterized in that one selects cationic (co) polymer (B) of polyvinylamine and linear and branched homopolymers of alkyleneimine.

13. A formulation according to any one of claims 10 to 12, characterized in that it has a heavy metal content below 0.05 ppm, based on the solids content of the formulation in question.

14. A formulation according to any one of claims 10 to 13, characterized in that one selects compound (A) from methyl glycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate and their salts.

15. A formulation according to any one of claims 10 to 14, characterized in that it contains:

in total in the range from 1 to 50% by weight of compound (A),

total in the range of 0.001 to 2% by weight of cationic (co) polymer (B), in the range of 1 to 30% by weight of silicate (C),

in total in the range of zero to 15% by weight of bleach (D) and

total in the range of zero to 5% by weight polyvinyl alcohol (E),

in each case based on solids content of the relevant formulation.

16. A formulation according to any one of claims 10 to 15, characterized in that silicate (C) has an average primary particle diameter in the range of 10 to 1000 nm.

17. A process for the preparation of formulations according to any one of claims 10 to 16, characterized in that one

(C) at least one silicate or water glass,

(E) optionally polyvinyl alcohol

mixed in one or more steps with each other in the presence of water and then partially removed the water.

18. The method according to claim 16, characterized in that the water is completely or partially removed by compaction, spray drying or spray granulation.