EP2768937A1 - Formulations, use thereof as or to produce dishwashing detergents, and production thereof - Google Patents

Abstract

The invention relates to formulations, containing (A) at least one compound, selected from aminocarboxylates and polyaminocarboxylates and salts and derivatives thereof, (B) at least one zinc salt, and (C) at least one homopolymer or copolymer of ethyleneimine.

Description

 Formulations, their use as or for the manufacture of dishwashing detergents and their preparation

The present invention relates to formulations containing

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

 (B) at least one zinc salt, and

 (C) at least one homo- or copolymer of ethyleneimine. 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. They must thoroughly clean the dishes, have no harmful or potentially harmful substances in the wastewater, allow the draining and drying of the water from the dishes, and 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.

From EP 2,118,254 it is known that zinc salts can be used in combination with certain vinyl polymers as inhibitors for the prevention of 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 the glass corrosion.

In WO 03/104370 it is proposed to use zinc-containing phyllosilicates in order to avoid glass corrosion. US Pat. No. 5,981,456 and WO 99/05248 disclose numerous dishwashing agents to which zinc salts or bismuth salts can be added in order to protect cutlery from tarnishing or corrosion. 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.

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.

Contain formulations 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) called, and their derivatives, and preferably salts.

Compound (A) can be present as the free acid or, preferably, in partially or completely neutralized form, ie as salt. As counterions, for example inorganic cations, such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg ^2+, more preferably Na ^+, K ^+, or organic cations, preferably substituted with one or more organic radicals ammonium, in particular triethanol ammonium, N, N- 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 one embodiment of the present invention, compound (A) is selected from derivatives of aminocarboxylates and polyaminocarboxylates, for example from their methyl or ethyl esters. 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, are partially or completely neutralized can 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 having at least two secondary amino groups each having a CH (COOH) CH 2 COOH group which, as mentioned above, may be partially or completely neutralized can.

Preferred polyaminocarboxylates (A) are selected from 1,2-diaminoethanetetraacetic acid (EDTA), iminodisuccinate (IDS), 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-COOH groups and tertiary ones

Are amino groups. It is possible to choose 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), nitrilotriacetic acid and glutamic acid diacetate and their derivatives and preferably their salts, in particular their sodium salts. Very particular preference is given to methylglycine diacetate and to the trisodium salt of MGDA.

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, zinc salts (B) of this kind are described as insoluble in water and 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, ZnC, ZnS0 ₄ , zinc acetate, zinc nitrate, Zn (NOs) 2,

Zn (CH ₃ SO ₃ ) ₂ and zinc gallate are preferred, ZnC, ZnSO ₄ , zinc acetate, zinc nitrate, Zn (NO 2) 2, Zn (CH ₃ SO ₃ ) ₂ and zinc gallate.

In another embodiment of the present invention, zinc salt (B) is selected from ZnO, ZnO-aq, Zn (OH) ₂ and ZnC0 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 be converted. Thus, for example, it is possible to use zinc acetate or ZnC for the preparation of 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 which does not complexed or complexed.

Zinc salt (B) is present in such inventive formulations, which are solid at room temperature, preferably in the form of particles, for example, have a mean diameter (number average) in the range of 10 nm to 100 μηη, preferably 100 nm to 5 μηη, 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.

The formulation according to the invention also contains

(C) at least one copolymer or, preferably, a homopolymer of ethyleneimine, together referred to in short as polyethyleneimine (C).

Copolymers of ethyleneimine (aziridine) with one or more higher homologues of ethylenimine, such as propyleneimine (2-methylaziridine), 1- or 2-butylenimine (2-ethylaziridine or 2,3-dimethylaziridine), for example with 0.01 to 75 mol% of one or more homologues 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, in each case 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.

In the context of the present invention, polyalkylenepolyamines are understood to mean those 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 dimers 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). 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:

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.

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 _v 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 chosen from dendrimers.

In one embodiment of the present invention, 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, 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 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, preferably from 1 to 30 ppm, determined according to Leach method "Heavy metals" in the context of the present invention are all metals with 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, as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-a-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.

Examples of suitable chlorine-containing bleaching agents are 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, one or more 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. sate 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 the} same or different selected from linear C ¹ -C 10 -alkyl, preferably 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: 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 is} selected from C 6 -C 20 -alkyl, in particular n-CsH-i, n-doH-i, n-C 12 H 25, n-Ci4H29, 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. Mixtures of several different nonionic surfactants may also be present.

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, phyllosilicates, especially those of the formula ## STR4 ## Na 2 Si 2 O, .beta.-Na 2 Si 2 O 5, and 5-Na 2 Si 2 O, furthermore citric acid and its alkali metal salts, succinic acid and its alkali metal salts, 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.

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 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 hydrophobically modified monomer, such as be 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 - Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C22-α-olefin, a mixture of C2o-C24-α-olefins and polyisobutene with 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 monomers containing sulfonic acid groups 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-propen-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2- Sulfoethylmethacrylat, 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 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 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, for example, 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, for example, 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, phloroglucinol 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 made of glass is understood to mean that the object in question has at least one piece of glass which comes into contact with the ambient air and, when the product is in use. may 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 glass.

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 according to the invention to clean glass together with metal objects, for example together with pots, pans or garlic presses.

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

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

 (B) at least one zinc salt,

 (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 completely or partially removed, for example, to a residual moisture in the range from zero to 5% by weight, from 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 from 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 dosage 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 which contained the starting materials 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

 Note: All quantities in g.

Abbreviations:

 MGDA: methylglycine diacetic acid as trisodium salt

 TAED: Ν, Ν, Ν ', Ν'-tetraacetylethylenediamine, disodium salt

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

I.2 Preparation of formulations according to the invention

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.

If one dosed the appropriate proportions of the base mixture separately from the aqueous solution of (A.1), (B) or (C) in the test dishwasher with endurance runner (or in the immersion test), the same results were obtained as when the dried formulation was used tested with equal amounts of drugs. So it does not depend on the order of the dosage.

(B.1): ZnSOv7 H2O. 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.

11.1 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 comparative 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 rinse cycles each, 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 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. II.2 Test method Immersion test

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

Test conditions:

Temperature: 75 ° C

Time: 72 hours

 5 liters of distilled water or water with defined water hardness ("hardness water")

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

Experimental procedure:

First, they rinsed for the purpose of pretreatment, the test pieces in a Haushaltsge- dishwashing machine (Bosch SGS5602) with a 1 g 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.

The stainless steel pot was filled with 5.5 liters of water and added 25 g of formulation or comparative 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 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 specimens were rinsed in the household dishwasher with a formulation consisting of 1 g of surfactant (n-CisH37 (OCH2CH2) ioOH) 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. In doing so, one judged the surface the test specimens with regard to line corrosion (glass scoring) and haze corrosion (surface 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: High haze over almost the entire glass surface. Intermediate notes (e.g., L3-4) were also allowed in the matching.

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.

Table 2: Results of tests with dishwasher (endurance runner)

Table 2 (continued): Results of tests with dishwasher (endurance runner)

Table 3: Immersion tests

Claims

claims: Formulation containing  (A) at least one compound selected from aminocarboxylates and polyaminocarboxylates and their salts and derivatives,  (B) at least one zinc salt, and  (C) at least one homo- or copolymer of ethyleneimine. Formulation according to claim 1, characterized in that it is free of phosphates and polyphosphates. Formulation according to Claim 1 or 2, characterized in that (C) is selected from homopolymers of ethyleneimine, linear or branched, and graft copolymers of ethyleneimine. A formulation according to any one of claims 1 to 3, characterized in that one selects zinc salt from ZnC, ZnS0 ₄ , zinc acetate, Zinkeitrat, Zn (NOs) 2, Zn (CH3S03) 2 and Zinkgallat. A formulation as claimed in any of claims 1 to 4, which comprises choosing compound (A) from methylglycine diacetate (MGDA), nitrilotriacetic acid and glutamic acid diacetate and salts and derivatives thereof. Formulation according to one of claims 1 to 5, characterized in that it is solid at room temperature. A formulation according to any one of claims 1 to 6, characterized in that it contains in the range of 0.1 to 10 wt .-% water. A formulation according to any one of claims 1 to 7, characterized in that it contains (D) at least one bleaching agent selected from oxygen bleaching agents and chlorine-containing bleaching agents. Formulation according to one of claims 1 to 8, characterized in that it contains:  in total in the range from 1 to 50% by weight of compound (A),  in total in the range of 0.05 to 0.4% by weight of zinc salt, indicated as Zn, and in total 0.05 to 2% by weight of homopolymer or copolymer of ethyleneimine (C),  optionally from 0.5 to 15% by weight of bleaching agent (D), in each case based on solids content of the relevant formulation. 10. Use of formulations according to one of claims 1 to 9 for the machine cleaning of dishes and kitchen utensils. 1 1. Use of formulations according to any one of claims 1 to 9 for machine cleaning of articles having at least one surface of glass which may be decorated or not decorated. 12. Use according to claim 10 or 1 1, characterized in that it is a mechanical cleaning to a rinse or cleaning with a dishwasher. 13. Use according to any one of claims 10 to 12, characterized in that at least one formulation according to any one of claims 1 to 9 for automated cleaning of drinking glasses, glass vases and glass jars is used for cooking. 14. A process for the preparation of formulations according to any one of claims 1 to 9,  characterized in that one  (A) at least one compound selected from aminocarboxylates and polyaminocarboxylates and their salts and derivatives,  (B) at least one zinc salt,  (C) at least one homo- or copolymer of ethyleneimine  (D) and optionally at least one bleaching agent selected from oxygen bleaching agents and chlorine-containing bleaching agents,  and optionally other ingredients in one or more steps mixed together in the presence of water and then removed the water. 15. The method according to claim 14, characterized in that the water is removed by spray drying, spray granulation or compaction.