EP2768937B1 - Formulations, their use as or for the manufacture of dishwashing agents and their manufacture - Google Patents

Description

1. (A) insgesamt im Bereich von 1 bis 50 Gew.-% mindestens einer Verbindung, gewählt aus Methylglycindiacetat (MGDA) und dem Trinatriumsalz von MGDA,
2. (B) insgesamt im Bereich von 0,05 bis 0,4 Gew.-% mindestens eines Zink-Salzes, und
3. (C) insgesamt 0,05 bis 2 Ges.-% mindestens eines Homo- oder Copolymer von Ethylenimin, und
4. (D) gegebenenfalls 0,5 bis 15 Gew.-% Bleichmittel (D),
   bezogen jeweils auf Feststoffgehalt der betreffenden Formulierung.

The present invention relates to formulations containing

1. (A) in total in the range of from 1 to 50% by weight of at least one compound selected from methylglycine diacetate (MGDA) and the trisodium salt of MGDA,
2. (B) in total in the range of 0.05 to 0.4 wt .-% of at least one zinc salt, and
3. (C) a total of 0.05 to 2 Ges .-% of at least one homo- or copolymer of ethyleneimine, and
4. (D) optionally 0.5 to 15% by weight of bleaching agent (D),
   in each case based on solids content of the relevant formulation.

Furthermore, the present invention relates to a process for the preparation of formulations according to the invention and their use as or for the production of dishwashing detergents, in particular dishwashing detergents for machine dishwashing.

Dishwashing detergents have many requirements to fulfill. So they have to clean the dishes thoroughly, they should have no harmful or potentially harmful substances in the wastewater, 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 rubbing 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.

Out EP 2 118 254 It is known that one can use zinc salts in combination with certain vinyl polymers as inhibitors to prevent glass corrosion.

In EP 0 383 482 It is proposed to use zinc salts with a particle diameter of less than 1.7 mm in order to reduce glass corrosion.

In WO 03/104370 It is proposed to use zinc-containing phyllosilicates in order to avoid glass corrosion.

Out US 5,981,456 and WO 99/05248 There are numerous dishwashing agents known to which zinc salts can be added to protect cutlery from tarnishing or corrosion.

Out WO 2002/64719 It is known that one can use certain copolymers of ethylenically unsaturated carboxylic acids with, for example, esters of ethylenically unsaturated carboxylic acids in dishwashing detergents.

Out 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.

In EP 1 721 962 A1 discloses a dishwashing detergent containing MGDA and zinc sulfate.

The glass corrosion, in particular the line corrosion and the turbidity, but is not sufficiently delayed or prevented in many cases.

It was therefore the object to provide formulations which are suitable as or for the production of dishwashing agents and which avoid the disadvantages known from the prior art and inhibit glass corrosion or at least reduce it 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 called formulations according to the invention.

1. (A) insgesamt im Bereich von 1 bis 50 Gew.-% mindestens einer Verbindung, gewählt aus Methylglycindiacetat (MGDA) und dem Trinatriumsalz von MGDA, im Rahmen der vorliegenden Erfindung kurz auch Aminocarboxylat (A) oder auch Verbindung (A) genannt.

Contain formulations according to the invention

1. (A) in total in the range of 1 to 50 wt .-% of at least one compound selected from methylglycine diacetate (MGDA) and the trisodium salt of MGDA, in the context of the present invention also briefly aminocarboxylate (A) or compound (A) mentioned.

Formulations according to the invention contain at least one zinc salt (B). Zinc salts (B) can be selected from water-soluble and non-water-soluble zinc salts. In the context of the present invention, such Zinc salts (B) referred to as not water-soluble, which have a solubility of 0.1 g / l or less in distilled water at 25 ° C. Zinc salts (B), which have a higher water solubility, are accordingly referred to in the context of the present invention as water-soluble zinc salts.

In one embodiment of the present invention, zinc salt (B) is selected from zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnCl ₂ , ZnSO ₄ , zinc acetate, zinc citrate, Zn (NO ₃ ) ₂ , Zn (CH ₃ SO ₃ ) ₂ and zinc gallate ZnCl ₂ , ZnSO ₄ , zinc acetate, zinc citrate, Zn (NO ₃ ) ₂ , Zn (CH ₃ SO ₃ ) ₂ and zinc gallate are preferred.

In another embodiment of the present invention, zinc salt (B) is selected from ZnO, ZnO-aq, Zn (OH) ₂ and ZnCO ₃ . ZnO-aq is preferred.

In one embodiment of the present invention, zinc salt (B) is selected from zinc oxides having an average particle diameter (weight average) in the range of 10 nm to 100 μm.

The cation in zinc salt (B) can be complexed, for example, complexed with ammonia ligands or water ligands, and especially present hydrated. To simplify the notation, ligands are usually omitted in the context of the present invention, if they are water ligands.

Depending on how to adjust the pH of mixture according to the invention, zinc salt (B) can convert. It is thus possible, for example, to use zinc acetate or ZnCl ₂ to prepare the formulation according to the invention, but this converts to ZnO, Zn (OH) ₂ or ZnO-aq at a pH of 8 or 9 in an aqueous environment can not be complexed or complexed.

Zinc salt (B) is present in such formulations according to the invention which are solid at room temperature, preferably in the form of particles having, for example, a number average molecular weight in the range of 10 nm to 100 μm, preferably 100 nm to 5 μm, determined, for example, by X-ray scattering.

Zinc salt (B) is present in such inventive formulations, which are liquid at room temperature, in dissolved or solid or in colloidal form.

• (C) insgesamt 0,05 bis 2 Gew.-% mindestens eines Copolymers oder vorzugsweise eines Homopolymers von Ethylenimin, zusammen kurz auch Polyethylenimin (C) genannt.

The formulation according to the invention also contains

• (C) a total of 0.05 to 2 wt .-% of at least one copolymer or, preferably, a homopolymer of ethyleneimine, together briefly also called polyethyleneimine (C).

For the purposes of the present invention, copolymers of ethyleneimine also include copolymers of ethyleneimine (aziridine) with one or more higher homologues of ethyleneimine, such as propyleneimine (2-methylaziridine), 1- or 2-butylenimine (2-ethylaziridine or dimethylaziridine) to understand, for example, with 0.01 to 75 mol% of one or more homologs of ethyleneimine, based on the proportion of ethyleneimine. However, preferred are those copolymers which contain only ethyleneimine and in the range of 0.01 to 5 mol% homologues of ethyleneimine in copolymerized form, and in particular homopolymers of ethyleneimine.

In one embodiment of the present invention, copolymers of ethyleneimine (C) are selected from graft copolymers of ethyleneimine (C). Such graft copolymers are also referred to in the context of the present invention as ethyleneimine graft copolymers (C). Ethyleneimine graft copolymers (C) may be crosslinked or uncrosslinked.

In one embodiment of the present invention, ethyleneimine graft copolymers (C) are selected from those polymers obtainable by grafting polyamidoamines with ethyleneimine. Preferably, ethyleneimine graft copolymers (C) are composed of 10 to 90% by weight of polyamidoamine as grafting base and 90 to 10% by weight of ethyleneimine as grafting support, each based on ethyleneimine graft copolymer (C).

Polyamidoamines are obtainable for example by condensation of polyalkylenepolyamines in pure form, as a mixture with one another or in a mixture with diamines.

For the purposes of the present invention, polyalkylenepolyamines are understood as meaning compounds which contain at least 3 basic nitrogen atoms in the molecule, for example diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N- (2-aminoethyl) -1,3-propanediamine and N , N'-bis (3-aminopropyl) ethylenediamine.

Examples of suitable diamines are 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, isophoronediamine, 4,4'-diaminodiphenylmethane, 1,4-bis ( 3-aminopropyl) piperazine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine and α, ω-diamino compounds of polyalkylene oxides.

In another embodiment of the present invention, ethyleneimine graft copolymers (C) are selected from those polymers which can be prepared by grafting polyvinylamines as a grafting base with ethyleneimine or oligomers of ethyleneimine, for example dimerren or trimers of ethyleneimine. Preferably, ethyleneimine graft copolymers (C) are composed of 10 to 90% by weight of polyvinylamine as grafting base and 90 to 10% by weight of ethyleneimine as grafting support, in each case based on ethyleneimine graft copolymer (C).

Preferably, however, at least one polyethyleneimine (C) in the form of a homopolymer, preferably uncrosslinked, is chosen as the component of the formulation according to the invention. According to a particular embodiment of the invention, polyethyleneimine (C) 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, polyethyleneimine (C) 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).

mit D (dendritisch) entsprechend dem Anteil tertiärer Aminogruppen, L (linear) entsprechend dem Anteil sekundärer Aminogruppen und T (terminal) entsprechend dem Anteil primärer Aminogruppen.In one embodiment of the present invention, polyethyleneimines (C) are selected from highly branched polyethyleneimines. Highly branched polyethylenimines (C) 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: $$\mathrm{DB}=\mathrm{D}+\mathrm{T}/\mathrm{D}+\mathrm{T}+\mathrm{L}$$

with D (dendritic) corresponding to the proportion of tertiary amino groups, L (linear) corresponding to the proportion of secondary amino groups and T (terminal) corresponding to the proportion of primary amino groups.

Polyethyleneimines (C) having DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90 and more preferably in the range from 0.30 to 0.80%, are considered highly branched polyethylenimines (C) within the scope of the present invention. and most preferably at least 0.5.

In the context of the present invention, polyethylene dendrimers (C) which are dendritic polyethylenimines (C) are understood as meaning polyethylenimines (C) having a structurally and molecularly uniform structure.

In one embodiment of the present invention, polyethylenimine (C) 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 (C) 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 is selected from dendrimers.

As mentioned above, formulations according to the invention contain
in total in the range from 1 to 50% by weight of compound (A), preferably 10 to 25% by weight, in total in the range from 0.05 to 0.4% by weight of zinc salt (B), preferably 0, 1 to 0.2 wt .-%, and
total in the range of 0.05 to 0.4 wt .-% zinc salt (B), preferably 0.1 to 0.2 wt .-%, and
a total of from 0.05 to 2% by weight of homopolymer or copolymer of ethyleneimine (C), preferably from 0.1 to 0.5% by weight,
optionally a total of 0.5 to 15% by weight of bleaching agent (D),
in each case based on solids content of the relevant formulation.

The proportion of zinc salt is given as zinc or zinc ions. This allows you to calculate the proportion of the counterion.

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 preparation or a gel.

In one embodiment of the present invention, the formulation according to the invention contains from 0.1 to 10% by weight of water, based on the sum of all solids of the relevant formulation.

Without wishing to give preference to any particular theory, it is possible that zinc salt (B) may be present in formulations of the invention which are complexed by polyethylenimine (C).

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 hexasodium metaphosphate. The term "free from" in connection with phosphates and polyphosphates in the context of the present invention should be understood to mean that the total content of phosphate and polyphosphate ranges 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, preferably from 1 to 30 ppm, determined according to Leach method.

In the context of the present invention, "heavy metals" are all metals having a specific density of at least 6 g / cm ³ , but not zinc. In particular, the heavy metals are precious metals and bismuth, iron, copper, lead, tin, nickel, cadmium and chromium. Preferably, formulation according to the invention contains no measurable proportions of bismuth compounds, that is to say, for example, less than 1 ppm.

In one embodiment of the present invention, formulation according to the invention contains one or more bleaching agents (D), for example one or more oxygen bleaching agents or one or more chlorine-containing bleaching agents.

For example, formulations according to the invention may contain from 0.5 to 15% by weight of bleach (D).

Examples of suitable oxygen bleaching agents are sodium perborate, anhydrous or, for example, monohydrate or tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-diperoxydodecanedioic acid , Perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as the free acid or as the alkali metal salt, in particular as the sodium salt, furthermore sulfonyl peroxyacids and cationic peroxyacids.

For example, formulations according to the invention may contain in the range of 0.5 to 15% by weight of oxygen bleach.

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

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

In one embodiment of the present invention, formulation according to the invention may comprise further ingredients (E), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more a plurality of 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, or several 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.

in der die Variablen wie folgt definiert sind:

R¹

gleich oder verschieden gewählt aus linearem C₁-C₁₀-Alkyl, bevorzugt Ethyl und besonders bevorzugt Methyl,

R²

gewählt aus C₈-C₂₂-Alkyl, beispielsweise n-C₈H₁₇, n-C₁₀H₂₁, n-C₁₂H₂₅, n-C₁₄H₂₉, n-C₁₆H₃₃ oder n-C₁₈H₃₇,

R³

gewählt aus C₁-C₁₀-Alkyl, Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, 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 oder iso-Decyl,

m und n liegen im Bereich von null bis 300, wobei die Summe von n und m mindestens eins beträgt. Bevorzugt ist m im Bereich von 1 bis 100 und n im Bereich von 0 bis 30.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

selected identically or differently from linear C ₁ -C ₁₀ -alkyl, preferably ethyl and particularly preferably methyl,

R ²

selected from C ₈ -C ₂₂ -alkyl, for example nC ₈ H ₁₇ , nC ₁₀ H ₂₁ , nC ₁₂ H ₂₅ , nC ₁₄ H ₂₉ , nC ₁₆ H ₃₃ or nC ₁₈ H ₃₇ ,

R ³

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 isodecyl,

m and n are in the range of zero to 300, where the sum of n and m is 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.

in der die Variablen wie folgt definiert sind:

R⁵

gleich oder verschieden und gewählt aus linearem C₁-C₄-Alkyl, bevorzugt jeweils gleich und Ethyl und besonders bevorzugt Methyl,

R⁴

gewählt aus C₆-C₂₀-Alkyl, insbesondere n-C₈H₁₇, n-C₁₀H₂₁, n-C₁₂H₂₅, n-C₁₄H₂₉, n-C₁₆H₃₃, n-C₁₈H₃₇.

a

eine Zahl im Bereich von 1 bis 6,

b

ist eine Zahl im Bereich von 4 bis 20,

d

ist eine Zahl im Bereich von 4 bis 25.

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

where the variables are defined as follows:

R ⁵

identical or different and selected from linear C ₁ -C ₄ -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,

R ⁴

selected from C ₆ -C ₂₀ -alkyl, in particular nC ₈ H ₁₇ , nC ₁₀ H ₂₁ , nC ₁₂ H ₂₅ , nC ₁₄ H ₂₉ , nC ₁₆ H ₃₃ , nC ₁₈ H ₃₇ .

a

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, formulation of the invention may contain in the range of from 3 to 20% by weight of surfactant.

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

Formulations according to the invention may contain, for example, up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, in each case based on the total solids content of the formulation according to the invention.

Formulations according to the invention may contain one or more builders, in particular phosphate-free builders. Examples of suitable builders are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, especially those of the formula α-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ , and δ-Na ₂ Si ₂ O ₅ , furthermore citric acid and their alkali metal salts, succinic acid and its alkali metal salts, fatty acid sulfonates, α-hydroxypropionic acid, alkali metal malates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example, polycarboxylates and polyaspartic acid.

In one embodiment of the present invention, builders of polycarboxylates are selected, 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 to use copolymers of at least one monomer selected from the group consisting of monoethylenically unsaturated C ₃ -C ₁₀ -mono- or 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 hydrophobic Monomers are used as enumerated below.

Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexadecene and 1-octadecene. Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C ₂₂ -α-olefin, a mixture of C ₂₀ -C ₂₄ -α-olefins and polyisobutene having an average of 12 to 100 carbon atoms.

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. The polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.

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 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 according to the invention may contain one or more co-builders.

Examples of co-builders are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. 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 one or more alkali carriers. Alkaline carriers, for example, provide the pH of at least 9 when an alkaline pH is desired. Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates. Preferred alkali metal is in each case potassium, particularly preferred is sodium.

Formulations of 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 manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.

Formulations according to the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile 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).

Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

Formulations of 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, phloroglucin or pyrogallol.

In one embodiment of the present invention, formulations according to the invention contain a total of in the range of 0.1 to 1.5 wt .-% corrosion inhibitor.

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

Formulations of 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 according to the invention contain in total in the range from 0.05 to 0.5% by weight defoamer.

In one embodiment of the present invention, formulations according to the invention may contain one or more acids, for example methanesulfonic acid.

In one embodiment of the present invention, formulations according to the invention have a pH in the range from 5 to 14, preferably 8 to 13.

Another object of the present invention is the use of formulations according to the invention for the automatic cleaning of dishes and kitchen utensils. As kitchen utensils in the context of the present invention, for example, pots, pans, casseroles to call, and metal objects such as, for example, skimmers, roasters and garlic presses.

Preferred is the use of formulations according to the invention for machine cleaning of articles which have at least one surface of 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 during use of the object can be contaminated. 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 metal handle.

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.

Machine cleaning is preferably dishwashing with a dishwasher (English: automatic dishwashing).

In one embodiment of the present invention, at least one formulation according to the invention for automated cleaning of drinking glasses, glass vases and glass jars is used 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 machine-cleaning formulations according to the invention are used, even with repeated mechanical cleaning of objects which have at least one surface made of glass, there is very little tendency for glass corrosion, even if objects comprising at least one surface made of glass are used have, along with heavily soiled cutlery or dishes cleans. In addition, it is much less harmful to use the formulation of the present invention to clean glass together with metal objects, such as pots, pans or garlic presses.

1. (A) mindestens eine Verbindung, gewählt aus Aminocarboxylaten und Polyaminocarboxylaten sowie deren Salzen und Derivaten,
2. (B) mindestens ein Zink-Salz,
3. (C) mindestens ein Homo- oder Copolymer von Ethylenimin

und gegebenenfalls weitere Inhaltsstoffe (E) in einem oder mehreren Schritten miteinander in Gegenwart von Wasser vermischt, beispielsweise verrührt, und anschließend das Wasser entfernt, und zwar vollständig oder zumindest teilweise.A further subject of the present invention is a process for the preparation of formulations according to the invention, in short also called production process according to the invention. For carrying out the preparation process according to the invention, it is possible, for example, to proceed in such a way that

1. (A) at least one compound selected from aminocarboxylates and polyaminocarboxylates and their salts and derivatives,
2. (B) at least one zinc salt,
3. (C) at least one homo- or copolymer of ethyleneimine

and optionally further ingredients (E) in one or more steps mixed together in the presence of water, for example, stirred, and then the water removed, completely or at least partially.

Compound (A), zinc salt (B) and polyethyleneimine (C) and bleaching agent (D) are defined above.

In one embodiment of the present invention, before at least partially removing the water, it is possible to mix with one or more other ingredients (E) for formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus free builder, one or more cobuilders, one or more alkali carriers, 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, with buffer or dye.

In one embodiment, the water is removed completely or partially, for example to a residual moisture in the range from zero to 5% by weight, from the formulation according to the invention by evaporation, in particular by spray drying, spray granulation or compaction.

In one embodiment of the present invention, the water is removed, in whole or in part, at a pressure in the range of 0.3 to 2 bar.

In one embodiment of the present invention, the water is removed, in whole or in part, at temperatures in the range of 60 to 220 ° C.

By means of the preparation process according to the invention, it is easy to obtain formulations according to the invention.

The cleaning formulations according to the invention can be provided in liquid or solid form, single- or multiphase, as tablets or in the form of other dosing units, packaged or unpackaged. The water content of liquid formulations can vary from 35 to 90% water.

The invention is illustrated by working examples.

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.

In the context of the present invention,% and ppm always denote wt .-% and wt ppm, unless expressly stated otherwise, and in the case of formulations according to the invention based on the total solids content.

I. Preparation of formulations according to the invention 1.1 Preparation of basic mixtures

First, base mixtures were prepared containing the feedstocks according to Table 1. The starting materials were mixed dry. Table 1: Basic mixtures for experiments with formulations according to the invention and comparative formulations Base 1 Base 2 Base 3 protease 2.5 2.5 2.5 amylase 1 1 1 nC ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₉ OH 5 5 5 Polyacrylic acid M _w 4,000 g / mol as sodium salt, completely neutralized 10 10 10 Sodium percarbonate (D.1) 10.5 10.5 10.5 TAED 4 4 4 Na ₂ Si ₂ O ₅ 2 2 2 Na ₂ CO ₃ 19.5 19.5 19.5 Sodium citrate dihydrate 0 22.5 30 HEDP 0.5 0.5 0.5 Note: All quantities in g.

• MGDA: Methylglycindiessigsäure als Trinatriumsalz
• TAED: N,N,N',N'-Tetraacetylethylendiamin, Dinatriumsalz
• HEDP: Dinatriumsalz der Hydroxyethan-(1,1-diphosphonsäure)

Abbreviations:

• MGDA: methylglycine diacetic acid as trisodium salt
• TAED: N, N, N ', N'-tetraacetylethylenediamine, disodium salt
• HEDP: disodium salt of hydroxyethane (1,1-diphosphonic acid)

I.2 Preparation of formulations according to the invention

• Zinksalz (B.1) oder (B.2) gemäß Tabelle 2 (oder 3)
• Polyethylenimin (C.1), (C.2) oder (C.3) gemäß Tabelle 2 (oder 3)

In a 100 ml beaker, 20 ml of distilled water were added and successively added with stirring:

• Zinc salt (B.1) or (B.2) according to Table 2 (or 3)
• Polyethyleneimine (C.1), (C.2) or (C.3) according to Table 2 (or 3)

The mixture was stirred for 10 minutes at room temperature. Then, MGDA trisodium salt (A.1) dissolved in 30 ml of water was added as shown in Table 2 (or 3). A clear solution was obtained. Thereafter, base mixture according to Table 2 (or 3) was added, stirred again, and the water evaporated.
There were obtained formulations according to the invention, which were tested according to Table 2 (or 3).

To prepare comparative formulations, the procedure was analogous, but omitting the zinc salt (B) or the polyethyleneimine (C) or both.

• (B.1): ZnSO₄·7 H₂O. Mengenangaben sind bezogen auf Zink.
• (B.2): ZnO. Mengenangaben sind bezogen auf Zink.
• (C.1): Polyethylenimin-Homopolymer, M_w 800 g/mol, DB = 0,63
• (C.2): Polyethylenimin-Homopolymer, M_w 5.000 g/mol, DB = 0,67
• (C.3): Polyethylenimin-Homopolymer, M_w 25.000 g/mol, DB = 0,70

If you dosed the corresponding proportions of base mixture separated from aqueous solution of (A.1), (B) or (C) in the test dishwasher with Dauerläufer (or immersion test), obtained the same results as when the dried formulation with the same Tested quantities of active ingredients. So it does not depend on the order of the dosage.

• (B.1): ZnSO ₄ .7H ₂ O. Quantities are based on zinc.
• (B.2): ZnO. Quantities are based on zinc.
• (C.1): Polyethyleneimine homopolymer, _Mw 800 g / mol, DB = 0.63
• (C.2): Polyethyleneimine homopolymer, M _w 5,000 g / mol, DB = 0.67
• (C.3): Polyethyleneimine homopolymer, M _w 25,000 g / mol, DB = 0.70

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

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

II.1 Test method Dishwasher with endurance runner

• Dishwasher: Miele G 1222 SCL
• Program: 65 ° C (with pre-rinse)
• Wash ware: 3 champagne glasses "GILDE", 3 shot glasses, "INTERMEZZO"

For cleaning, the glasses were placed in the upper basket of the dishwasher. The dishwashing agent used was in each case 25 g of formulation according to the invention or comparison formulation according to Table 2, where Table 2 individually specifies the active components (A.1), optionally (B), optionally (C) and base mixture of formulation according to the invention. 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 rinsing cycles, ie, 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 washware was given after 100 cycles in a darkened chamber under light behind a pinhole using a grading scale from 1 (very poor) to 5 (very good). In each case grades for area corrosion / turbidity or line corrosion were determined.

11.2 Test method Immersion test

• Edelstahltopf (Volumen ca. 6 Liter) mit Deckel mit Loch für Kontaktthermometer
• Gitterbodeneinsatz mit Halterung für den Edelstahltopf
• Magnetrührer mit Rührstäbchen, Kontaktthermometer, Gummistopfen mit Loch

Equipment:

• Stainless steel pot (volume approx. 6 liters) with lid with hole for contact thermometer
• Grid bottom insert with holder for the stainless steel pot
• Magnetic stirrer with stirrer, contact thermometer, rubber stopper with hole

• Temperatur: 75°C
• Zeit: 72 Stunden
• 5 Liter destilliertes Wasser oder Wasser mit definierter Wasserhärte ("Härtewasser")

Test conditions:

• Temperature: 75 ° C
• Time: 72 hours
• 5 liters of distilled water or water with defined water hardness ("hardness water")

The test specimens were each a champagne glass and a shot glass from the company Libbey (NL), a, material: soda-lime glasses.

Experimental procedure:

First, for the purpose of pretreatment, the specimens were rinsed in a domestic dishwasher (Bosch SGS5602) with a 1 g surfactant (nC ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH) and 20 g citric acid to remove any impurities. The test pieces were dried, their weight determined and fixed on the grid floor insert.

The stainless steel pot was filled with 5.5 liters of water and added 25 g of formulation or comparison formulation according to the invention, wherein Table 3 shows the active components (A.1), optionally (B), optionally (C) and base mixture of formulation according to the invention or comparison formulation each individually specified. The resulting cleaner liquor was stirred by means of the magnetic stirrer at 550 revolutions per minute. They installed the contact thermometer and covered the stainless steel pot with the lid, so that no water could evaporate during the experiment. It was heated to 75 ° C and put the grid bottom insert with the two specimens in the stainless steel pot, taking care that the specimens were completely immersed in the liquid.

After completion of the experiment, the test pieces were taken out and rinsed under running distilled water. Thereafter, the test pieces were rinsed in the domestic dishwasher with a formulation consisting of 1 g of surfactant (nC ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH) and 20 g of citric acid again with the 55 ° C program to remove any deposits ,

To assess the gravimetric removal, the dry specimens were weighed. This was followed by the visual assessment of the test specimens. Here it was judged the surface the test specimen with regard to line corrosion (glass scoring) and haze corrosion (area-like haze).

The assessments were made according to the following scheme.

• L5: keine Linien zu erkennen
• L4: in sehr wenigen Bereichen geringe Linienbildung, feine Linienkorrosion
• L3: in einigen Bereichen Linienkorrosion
• L2: in mehreren Bereichen Linienkorrosion
• L1: Stark ausgeprägte Linienkorrosion

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

• T5: no haze visible
• T4: low turbidity in very few areas
• T3: cloudiness in some areas
• T2: turbidity in several areas
• T1: 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 Tables 2 and 3. <b> Table 2: Results of Tests with Dishwasher (Endurance Runner) </ b> example Base mixture: [g] (A.1) [g] (B) [ml] (C) [mg] Weight loss champagne glass [mg] Weight loss shot glass [mg] Visual rating champagne glass Visual rating shot glass V-1 Base 1: 13.75 11.25 --- --- 60.1 26 L1, T1 L1, T2 V-2 Base 2: 19.37 5.63 --- --- 42.8 23 L1-2, T2 L2, T2 V-3 Base 3: 21.25 3.75 --- --- 36.7 19 L2, T2-3 L2, T2 V-4 Base 3: 21.25 3.75 240 (B.1) --- 11 6 L4, T4 L4, T4-5 V-5 Base 3: 21.25 3.75 120 (B.1) --- 16 7 L4, T4-5 L4, T4 V-6 Base 3: 21.25 3.75 40 (B.1) --- 24 11 L3, T2-3 L3, T2 7 Base 3: 21.25 3.75 80 (B.1) 130 (C.1) 4.8 2.6 L5, T5 L5, T5 8th Base 3: 21.25 3.75 80 (B.1) 130 (C.2) 5.7 2.7 L5, T5 L5, T5 9 Base 3: 21.25 3.75 80 (B.1) 130 (C.3) 7.2 3.1 L5, T4-5 L4-5, T4-5 10 Base 3: 21.25 3.75 80 (B.1) 65 (C.1) 6.9 3.2 L5, T5 L4-5, T5 11 Base 3: 21.25 3.75 80 (B.1) 65 (C.2) 7.4 3.9 L5, T4-5 L4-5, T4-5 12 Base 3: 21.25 3.75 80 (B.1) 65 (C.3) 8.6 4.2 L4-5, T4-5 L4-5, T4-5 13 Base 3: 21.25 3.75 40 (B.1) 65 (C.1) 5.2 2.6 L4-5, T5 L5, T5 14 Base 3: 21.25 3.75 40 (B.1) 65 (C.2) 6 2.7 L4-5, T5 L4-5, T5 15 Base 3: 21.25 3.75 40 (B.1) 65 (C.3) 7.3 3.6 L4-5, T4-5 L4-5, T5 16 Base 3: 21.25 3.75 40 (B.1) 32 (C.1) 7.1 4.4 L5, T4 L5, T4-5 17 Base 3: 21.25 3.75 40 (B.1) 32 (C.2) 7.4 4.7 L4-5, T4-5 L4,5, T4 18 Base 3: 21.25 3.75 20 (B.1) 32 (C.1) 6 3.4 L5, T4-5 L5, T5 19 Base 3: 21.25 3.75 20 (B.1) 32 (C.2) 6.8 3.9 L5, T4-5 L5, T5 20 Base 3: 21.25 3.75 20 (B.1) 16 (C.1) 6.8 4.1 L4-5, T4-5 L4-5, T4-5 21 Base 3: 21.25 3.75 20 (B.1) 16 (C.2) 7.8 4.8 L4, T4-5 L4, T4-5 22 Base 2: 19.37 5.63 40 (B.1) 32 (C.1) 9.4 6.8 L4, T4 L4-5, T4 example Base mixture [g] (A.1) [g] (B) [mg] (C) [mg] Weight loss champagne glass [mg] Weight loss shot glass [mg] Visual rating champagne glass Visual rating shot glass 23 Base 3: 21.25 3.75 80 (B.2) 32 (C.1) 6.9 4.2 L4, T4-5 L4, T4 24 Base 3: 21.25 3.75 40 (B.2) 32 (C.1) 7.3 4.3 L4, T4 L4, T4 25 Base 3: 21.25 3.75 20 (B.2) 32 (C.1) 7.8 4.9 L4, T4 L4, T4 example Base mixture, [g] (A.1) [g] (B) [mg] (C) [mg] Weight loss champagne glass [mg] Weight loss shot glass [mg] Visual rating champagne glass Visual rating schnapps glass VI.1 Base 3: 21.25 3.75 --- --- 169.20 95.10 L2, T2 L2, T3 VI.2 Base 3: 21.25 3.75 40 --- 118.60 63.70 L3, T2-3 L3, T3 VI.3 Base 3: 21.25 3.75 240 --- 74.60 41,00 L3-4, T3-4 L4, T3-4 I.4 Base 3: 21.25 3.75 30 48 (C.1) 49,40 26,30 L3-4, T4-5 L4-5, T4-5 I.5 Base 3: 21.25 3.75 30 48 (C.2) 76.70 40.40 L3-4, T4 L3-4, T3-4 I.6 Base 3: 21.25 3.75 40 65 (C.1) 42.50 23,60 L4, T4-5 L4-5, T4-5 I.7 Base 3: 21.25 3.75 40 65 (C.2) 61,90 32,00 L3-4, T4 L3-4, T3-4 I.8 Base 3: 21.25 3.75 80 130 (C.1) 41,90 22.00 L4, T4-5 L4-5, T4-5 I.9 Base 3: 21.25 3.75 80 130 (C.2) 58,90 30,60 L3-4, T4 L3-4, T3-4 I.10 Base 3: 21.25 3.75 240 390 (C.1) 28.40 15,30 L4-5, T5 L4-5, T5 I.11 Base 3: 21.25 3.75 240 390 (C.2) 34,50 18.20 L4-5, T4-5 L4, T4-5

Claims (13)

1. A formulation comprising

   (A) in total in the range from 1 to 50% by weight of at least one compound selected from methylglycinediacetate (MGDA) and the trisodium salt of MGDA,

   (B) in total in the range from 0.05 to 0.4% by weight of at least one zinc salt, given as Zn,

   (C) in total 0.05 to 2% by weight of at least one homopolymer or copolymer of ethyleneimine, and

   (D) optionally 0.5 to 15% by weight of bleach (D),
   based in each case on the solids content of the formulation in question.
2. The formulation according to claim 1, which is free from phosphates and polyphosphates.
3. The formulation according to claim 1 or 2, wherein (C) is selected from homopolymers of ethyleneimine, linear or branched, and graft copolymers of ethyleneimine.
4. The formulation according to any one of claims 1 to 3, wherein zinc salt is selected from ZnCl₂, ZnSO₄, zinc acetate, zinc citrate, Zn(NO₃)₂, Zn(CH₃SO₃)₂ and zinc gallate.
5. The formulation according to any one of claims 1 to 4, which is solid at room temperature.
6. The formulation according to any one of claims 1 to 5, which comprises water in the range from 0.1 to 10% by weight.
7. The formulation according to any one of claims 1 to 6, which comprises

   (D) at least one bleach selected from oxygen bleaches and chlorine-containing bleaches.
8. The use of formulations according to any one of claims 1 to 7 for the machine cleaning of crockery and kitchen utensils.
9. The use of formulations according to any one of claims 1 to 7 for the machine cleaning of objects which have at least one surface made of glass, which can be decorated or undecorated.
10. The use according to claim 8 or 9, wherein the machine cleaning is washing or cleaning using a dishwasher.
11. The use according to any one of claims 8 to 10, wherein at least one formulation according to any one of claims 1 to 7 is used for the machine cleaning of drinking glasses, glass vases and glass vessels for cooking.
12. A process for the preparation of formulations according to any one of claims 1 to 7, wherein

    (A) at least one compound selected from methylglycinediacetate (MGDA) and the trisodium salt of MGDA,

    (B) at least one zinc salt,

    (C) at least one homopolymer or copolymer of ethyleneimine

    (D) and optionally at least one bleach selected from oxygen bleaches and chlorine-containing bleaches,
    and optionally further ingredients are mixed in one or more steps with one another in the presence of water, and then the water is removed.
13. The process according to claim 12, wherein the water is removed by spray-drying, spray-granulation or compaction.