EP2841549A1

EP2841549A1 - Formulations, use thereof as or for production of dishwashing detergents and production thereof

Info

Publication number: EP2841549A1
Application number: EP13720303.0A
Authority: EP
Inventors: Alejandra Garcia Marcos; Stephan Hüffer; Markus Hartmann; Heike Weber; Mario Emmeluth
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2012-04-25
Filing date: 2013-04-23
Publication date: 2015-03-04
Anticipated expiration: 2033-04-23
Also published as: EP2841549B1; KR102007148B1; JP6133971B2; MX2014013009A; CA2871210A1; BR112014026565A2; JP2015515531A; PL2841549T3; KR20150013593A; CN104379717A; CN104379717B; RU2623440C2; ES2693772T3; RU2014147082A; WO2013160301A1; ES2612342T3

Abstract

Formulations comprising (A) at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and salts and derivatives thereof, and (B) at least one alkoxylated alkyleneimine polymer having a mean molecular weight M_w in the range from 800 to 25 000 g/mol, which has a positive charge density of at least 5 meq/g and which has in the range from 2 to not more than 80% by weight of alkylene oxide side chains, based on overall alkoxylated alkyleneimine polymer.

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 aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and (B) at least one alkoxylated alkyleneimine polymer having an average molecular weight Mw in the range from 800 to 25,000 g / mol having a positive charge density of at least 5 meq / g and having in the range of 2 to at most 80 wt .-% alkylene oxide side chains, based on the total alkoxylated alkyleneimine polymer.

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 agents, in particular dishwasher detergents for automatic 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 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, one can often observe a general cloudiness, for example a roughening, which makes the glass in question look unaesthetic. Overall, such effects are also subdivided into iridescent discoloration, scoring and surface and annular opacities.

WO 2006/108857 discloses alkoxylated polyethyleneimines as additives to detergents. Detergents containing zeolites or polyaminocarboxylates such as EDTA or triethylenediamine pentaacetate as complexing agents are disclosed by way of example. WO 01/96516 proposes formulations containing alkoxylated polyethylenimine for cleaning hard surfaces. For rinsing, purified water is used. From WO 2010/020765 dishwashing agents are known which contain polyethyleneimine. Such dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion. Zinc and bismuth-containing dishwashing detergents are not recommended. However, glass corrosion, in particular line corrosion and turbidity, is in many cases not sufficiently delayed or prevented.

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.

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

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

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

(A) at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and salts thereof, in the context of the present invention also referred to as aminocarboxylate (A) or compound (A), and preferably their salts.

Preference is given to choosing compound (A) as the free acid, particularly preferably in partially or completely neutralized form, ie as salt. As counter ions, for example, inorganic cations, for example ammonium, alkali or alkaline earth metal, preferably Mg ²⁺ , Ca ²⁺ , Na ⁺ , K ⁺ , or organic cations, preferably ammonium substituted with one or more organic radicals, in particular triethanolammonium, Ν, Ν-diethanolammonium, N-mono-C 1 -C 4 -alkyldiethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N, N-di-C 1 -C 4 -alkylethanolammonium.

Very particularly preferred compounds (A) are the alkali metal salts, in particular the sodium salts of methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GL DA).

Very particular preference is given to fully neutralizing methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) or glutamic acid diacetate (GLDA).

Formulations according to the invention also contain

(B) at least one alkoxylated alkyleneimine polymer having an average molecular weight M _w in the range from 800 to 25,000 g / mol, which has a positive charge density of at least 5 meq / g and which is in the range from 2 to a maximum of 80% by weight, preferably 5 to 60 wt .-% alkylene oxide side chains, based on the total alkoxylated alkyleneimine polymer.

Such modified alkyleneimine polymers are also briefly referred to as modified polyalkyleneimine (B) in the context of the present invention.

In the context of the present invention, alkyleneimine polymers are to be understood as meaning those polymeric materials which are obtained by homo- or copolymerization of one or more cyclic imines or by grafting a (co) polymer with at least one cyclic imine. Examples are polyalkylenepolyamines and polyamidoamines grafted with ethyleneimine. For the purposes of the present invention, polyalkylene polyamines are preferably understood as meaning those polymers which contain at least six nitrogen atoms and at least five C 2 -C 10 -alkylene units, preferably C 2 -C 3 -alkylene units per molecule, for example pentaethylenehexamine, and in particular polyethyleneimines. Alkyleneimine polymer and especially polyethyleneimine may have, for example, an average molecular weight (M _w ) of at least 300 g / mol, preferably the average molecular weight of polyethylenimine is in the range from 800 to 20,000 g / mol, determined by light scattering.

Polyalkylenepolyamines can be covalently modified in partially quaternized (alkylated) form as Alkylenimin- polymer. Suitable quaternizing agents (alkylating agents) are, for example, alkyl halides, in particular C 1 -C 10 -alkyl chloride, such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, n-butyl chloride, tert-butyl chloride, n-hexyl chloride, furthermore epichlorohydrin, dimethyl sulfate, diethyl sulfate and benzyl chloride. If quaternized (alkylated) polyalkylenepolyamines are covalently modified as the alkyleneimine polymer, the degree of quaternization (alkylation) is preferably 1 to 25, particularly preferably up to 20 mol%, based on quaternizable (alkylatable) N atoms in alkyleneimine. Polymer.

Furthermore, polyamidoamines grafted with ethyleneimine are suitable as alkyleneimine polymers. Suitable polyamidoamines are obtainable, for example, by reacting C 4 -C 10 -dicarboxylic acids with polyalkylenepolyamines, which preferably contain from 3 to 10 basic nitrogen atoms in the molecule. Examples of suitable dicarboxylic acids are succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is also possible to use mixtures of the abovementioned dicarboxylic acids, for example mixtures of adipic acid and glutaric acid or mixtures of maleic acid and adipic acid. Adipic acid is preferably used for the preparation of polyamidoamines. Suitable polyalkylenepolyamines which are condensed with the abovementioned dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine. The abovementioned polyalkylenepolyamines can also be used in the form of mixtures in the preparation of polyamidoamine. The preparation of polyamidoamine is preferably carried out in bulk, but may also be carried out in inert solvents, if appropriate. The condensation of dicarboxylic acid with polyalkylenepolyamine takes place at higher temperatures, for example in the range from 120 to 220.degree. The water formed during the reaction is distilled off from the reaction mixture. The condensation may optionally be carried out in the presence of lactones or lactams of carboxylic acids having 4 to 8 carbon atoms. In general, from 0.8 to 1.4 mol of a polyalkylenepolyamine are used per mole of dicarboxylic acid. Thus obtainable polyamidoamines have primary and secondary NH groups and are soluble in water.

Polyamidoamines grafted with ethyleneimine can be prepared by allowing ethyleneimine to act on polyamidoamine described above in the presence of Bronsted acids or Lewis acids, for example sulfuric acid, phosphoric acid or boron trifluoride etherate.

As a result, ethyleneimine is grafted onto the relevant polyamidoamine. For example, per basic nitrogen atom in the polyamidoamine, one can graft 1 to 10 ethyleneimine units, i. H. to 100 parts by weight of polyamidoamine is used about 10 to 500 parts by weight of ethyleneimine.

Preferred alkyleneimine polymer is polyethyleneimine.

In one embodiment of the present invention, polyethyleneimines are selected from highly branched polyethyleneimines. Highly branched polyethylenimines are characterized by their high degree of branching (DB). The degree of branching can be determined, for example, by ¹³ C-NMR spectroscopy, preferably in D 2 O, and is defined as follows: DB = D + T / D + T + L with D (dendritic) corresponding to the proportion of tertiary amino groups, L (linear) corresponding to the fraction of secondary amino groups and T (terminal) corresponding to the proportion of primary amino groups.

In the context of the present invention, highly branched polyethyleneimines are polyethylene imines having DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90, more preferably in the range from 0.30 to 0.80 and very particularly preferably at least 0.5.

In one embodiment of the present invention, polyethylenimine is highly branched polyethyleneimines (homopolymers) having an average molecular weight M _w in the range from 600 to 20,000 g / mol, preferably in the range from 800 to 15,000 g / mol.

Alkyleneimine polymer is used in the context of the present invention in covalently modified form, specifically in the range from 2 to 80% by weight, preferably from 5 to 60% by weight, of alkylene oxide side chains, based on the total alkoxylated alkyleneimine Polymer (B). For the alkoxylation can be used epoxides, for example ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2,3-butylene oxide, styrene oxide or epichlorohydrin. Preferred alkoxylation reagents are ethylene oxide and propylene oxide and mixtures of ethylene oxide and propylene oxide.

In one embodiment, alkoxylated alkyleneimine polymer (B) alkoxylates in the range of 5 to 60 mole percent of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer.

In one embodiment of the present invention, modified polyalkyleneimine (B) is selected from polyethyleneimines reacted with ethylene oxide or propylene oxide.

Modified polyalkyleneimine (B) can have as counter ions high molecular weight or low molecular weight anions, organic or preferably inorganic. High molecular weight anions in the context of the present invention have an average molecular weight of 200 g / mol or more, for example up to 2500 g / mol, low molecular weight anions have a molecular weight of less than 200 g / mol, for example from 17 to 150 g / mol. Examples of low molecular weight organic counterions are acetate, propionate and benzoate. Examples of low molecular weight inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate and bicarbonate. In one embodiment of the present invention, modified polyalkyleneimine (B) has a cationic charge density of at least 5 meq / g to a maximum of 25 meq / g (milliequivalents / g), preferably to 22 meq / g, where g is modified polyalkyleneimine (B) without taking into account the counterions. The cationic charge density can be determined, for example, by titration, for example with polyvinyl sulfate solution.

In one embodiment of the present invention, modified polyalkyleneimine (B) has a molecular weight distribution M _w / M _n in the range of 1.1 to 10, preferably 1.5 to 5.

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

total in the range of 1 to 50% by weight of aminocarboxylate (A), preferably 10 to 25% by weight, in total in the range of 0.001 to 5% by weight of modified polyalkyleneimine (B), preferably 0.02 to 0.5 % By weight, based in each case on the solids content of the relevant formulation. In a variant of the present invention, formulation according to the invention contains compound (A) and modified polyalkyleneimine (B) in a weight ratio in the range from 1000 to 1 to 25 to 1.

In a preferred embodiment of the present invention, formulation according to the invention is free of phosphates and polyphosphates, with hydrogen phosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexanatrium ummetaphosphate. In the context of the present invention, the term "free from", in the context of phosphates and polyphosphates, is understood to mean that the total content of phosphate and polyphosphate ranges from 10 ppm to 0.2% by weight, determined by gravimetry.

Formulations of the invention may contain other components which are advantageous, for example, for use in washing dishes and / or kitchen utensils. In another embodiment of the present invention formulations according to the invention contain no further components, which are advantageous, for example, for use in dishwashing and / or kitchen utensils, but can easily be formulated with further components and are therefore suitable as starting material. In one embodiment of the present invention formulations according to the invention contain sodium citrate (C). The term sodium citrate comprises the mono- and preferably the disodium salt with. Sodium citrate can be used as anhydrous salt or as a hydrate, for example as a dihydrate.

In one embodiment of the present invention formulations according to the invention contain (D) at least one compound chosen from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, in the context of the present invention also referred to as "bleaching agent (D)." Preferred bleaching agents (D) are selected from sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called Dihydrate, sodium percarbonate, anhydrous or, for example, as a monohydrate, and sodium persulfate, wherein the term "persulfate" in each case comprises the salt of the peracid H2SO5 and the peroxodisulfate with. The alkali metal salts may each also be alkali metal hydrogencarbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulphate. However, preference is given in each case to the dialkali metal salts.

In one embodiment of the present invention, formulation according to the invention comprises zero to 50% by weight of sodium citrate (C), preferably 1 to 30% by weight, particularly preferably at least 5% by weight of sodium citrate (C), determined as anhydrous sodium citrate,

a total of zero to 15% by weight of bleaching agent (D), preferably at least 0.5% by weight of bleaching agent (D), selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.

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

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.

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 bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more perfumes, one or more organic solvents, one or more several tabletting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizers.

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

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

where the variables are defined as follows:

R ^{1 is} identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case the same and ethyl and particularly preferably methyl, R ^{2 is} selected from C 1 -C 22 -alkyl, for example nC & Hn, n-doF i, n-C 12H 25, nC-uF s), n-Ci6H33 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 range from zero to 300, with 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) where the variables are defined as follows:

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

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 comprise, in addition to sodium citrate (C), one or more builders, in particular phosphate-free builders. Examples of suitable builders are silicates, especially sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the formula a-Na 2 Si 2 O, β-Na 2 Si 2 O, and 5-Na 2 Si 2 O, furthermore fatty acid sulfonates, α-hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl- and alkenyl disuccina tartaric acid, tartaric acid acetate, 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 C 4 -C 10 -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 a hydrophilic or hydrophobically modified 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 - Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C22-α-olefin, a mixture of C2o-C24-α-olefins and polyisobutene having an average of 12 to 100 carbon atoms per molecule. Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples which may be mentioned are: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate. Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.

Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2 hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and salts of said acids, such as their sodium, potassium or ammonium salts. Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.

In addition, amphoteric polymers can also be used as builders.

Formulations 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 according to the invention may contain, in addition to bleaching agent (D), one or more chlorine-containing bleaching agents. Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

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

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 carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands can also be used. such as cobalt, iron, copper and ruthenium amine complexes are useful 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 from 0.05 to 0.5% by weight of defoamer.

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

Preference is given to the use of formulations according to the invention for the automated cleaning of objects which have at least one surface made of glass, which decoratively or not decorated. In the context of the present invention, a surface of glass is to be understood as meaning that the object in question has at least one piece of glass which comes into contact with the ambient air and can be contaminated when the object is used. Thus, the objects in question may be those that are essentially glassy, 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, preferably a dishwasher with 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.

Also for rinsing water with a hardness in the range of 1 to 30 ° dH, preferably 2 to 25 ° dH can be used.

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.

Furthermore, it can be observed that formulations according to the invention when used for rinsing dishes and kitchen utensils and glass surfaces have a very good bleaching action. 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) aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and

(B) at least one alkoxylated alkyleneimine polymer having an average molecular weight Mw in the range of 800 to 25,000 g / mol, which has a positive charge density of at least 5 meq / g and in the range of 2 to at most 80 wt .-% alkylene oxide - Has side chains, based on the total alkoxylated alkyleneimine polymer, and optionally

(C) sodium citrate or

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

and optionally further components (E) are mixed together in one or more steps in the presence of water and then the water is completely or partially removed.

Compound (A), modified polyalkyleneimine (B) and bleaching agent (D) are defined above.

In one embodiment of the present invention, before at least partially removing the water, one may 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, one or more builders several co-builders, in particular phosphorus-free builders, one or more alkali carriers, one or more bleaches, 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 0.1 to 10% by weight of 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 from 60 to 220.degree. 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.

Data in% are wt .-%, unless expressly stated otherwise.

I. Preparation of formulations according to the invention The charge density of modified polyethylenimines (B) was always determined as follows (see also: Horn, Prog. Colloid & Polym., Sci. 1978, 65, 251):

1 g of the respective modified polyethyleneimine (B) was dissolved in 100 ml of demineralized water. A pH of 4.0 was set with a buffer solution and aqueous HCl, determined to be potentiometric. Three ml of an aqueous solution of toluidine blue (50 mg / l water) was added and titrated N / 400-KPVS (potassium polyvinyl sulfate) solution (Wako) with a concentration of 0.0004 meq / ml to a color change of blue pink. The charge density was calculated as follows: LA = 0.4 ^■ KV

LA: charge density of the relevant modified polyethyleneimine (B), meq / g (milliequivalent / g)

KV: consumption of N / 400 KPVS solution [ml]

1.1 Preparation of basic mixtures

First, base mixtures were prepared from 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

All information in g. Abbreviations:

MGDA: methylglycine diacetic acid as trisodium salt

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

I.2 Preparation of formulations according to the invention

1.2.1 Preparation of Formulations 2 to 8 According to the Invention and Comparative Formulations V1

Modified polyethylenimines (B) according to Table 2 were used which had been prepared according to the following general procedure:

In a 2-liter autoclave polyethyleneimine according to Table 2, column 2 and 3 and 0.7 wt .-% KOH cookie, water content 50 wt .-%, balance KOH), based on polyethyleneimine were submitted. The mixture was heated under reduced pressure (10 mbar) to 120 ° C and stirred for 2 hours at 120 ° C, with the removal of the water. Thereafter, the autoclave was purged three times with nitrogen and then heated to 140 ° C at an initial pressure of 1 bar. Then, over a period of 2 hours, either ethylene oxide or propylene oxide according to Table 2, column 5 was added. After complete addition, the mixture was stirred for a further 3 hours at 140 ° C. Thereafter, water or optionally other volatile compounds were removed under reduced pressure (10 mbar) at 90.degree. Modified polyethyleneimines (B) according to Table 2 were obtained as pale yellow waxy solids. Table 2: Modified polyethylenimines (B)

Abbreviations in Table 2:

AO: alkylene oxide

Column 2: M _w PEI refers to the molecular weight of the polyethylenimine used for the alkoxylation, ie to unmodified polyethyleneimine.

Column 3: PEI refers to unmodified polyethyleneimine.

Column 7: the molar proportions refer to the input substances.

Column 8: Weight fraction of alkylene oxide in the respective total alkoxylated alkyleneimine polymer (B).

Action:

In a 100 ml beaker, 20 ml of distilled water was added and modified polyethyleneimine (B) according to Tables 2 and 3 added with stirring.

Then it was stirred for 10 minutes. Then, MGDA trisodium salt (A.1) dissolved in 30 ml of water was added as shown in Table 3. A clear solution was obtained. Thereafter, base mixture according to Table 3 was added, stirred again and evaporated the water. If one dosed in the test, the appropriate proportions base mixture separately from aqueous solution of (A.1), (B), (C.1) or (D.1), gave 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. II. Use of formulations according to the invention and comparative formulations for machine cleaning of glasses

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

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

11.1 Test method Dishwasher with endurance runner

Dishwasher: Miele G 1222 SCL

Program: 65 ° C (with pre-rinse)

Wash ware: 3 champagne glasses "GILDE", 3 shot glasses, "INTERMEZZO"

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

First, they rinsed for the purpose of pretreatment, the test pieces in a domestic dishwashing machine (Bosch SGS5602) with 1 g of surfactant (n-Ci8H37 (OCH ₂ CH ₂₎ ioOH) and 20 g of citric acid, to remove any impurities. The test pieces were dried, their weight determined and fixed on the grid floor insert. To assess the gravimetric removal, the dry specimens were weighed. This was followed by the visual assessment of the test specimens. The surface of the test specimens was evaluated for line corrosion (glass scoring) and haze corrosion (areal haze).

The assessments were made according to the following scheme.

Line corrosion:

L5: no lines to recognize

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

L3: line corrosion in some areas

L2: line corrosion in several areas

L1: Strong line corrosion. Glass opacity

L5: no haze visible

L4: low turbidity in very few areas

L3: cloudiness in some areas

L2: cloudiness in several areas

L1: markedly turbid over almost the entire glass surface

Interim scores (e.g., L3-4) were also allowed on the match.

If, instead of water, hardness water at 2 ° dH was used for the tests, formulations according to the invention were also always superior to the corresponding comparative formulations with regard to the inhibition of glass corrosion.

II.3 Results

The results are summarized in Table 3.

Table 3: Results of tests with dishwasher (endurance runner)

In the examples according to the invention, only little or no glass corrosion could always be determined.

Claims

claims

Formulation that is free of heavy metals, containing

(A) at least one aminocarboxylate selected from methylglycine diacetate (MGDA), imidoduccinic acid (IDS) and glutamic acid diacetate (GLDA) and salts thereof,

(B) at least one alkoxylated alkyleneimine polymer having an average molecular weight Mw in the range from 800 to 25,000 g / mol, which has a positive charge density of at least 5 meq / g and which is in the range from 2 to a maximum of 80% by weight of alkylene oxide. Has side chains, based on the total alkoxylated alkyleneimine polymer.

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

A formulation according to claim 1 or 2, characterized in that (B) is selected from polyethyleneimines which are reacted with ethylene oxide or propylene oxide.

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

A formulation according to any one of claims 1 to 4, characterized in that alkyleneimine polymer (B) is selected from those in which a maximum of 30 mol% of the nitrogen atoms of the alkyleneimine polymer are reacted with propylene oxide.

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 the molar ratio of nitrogen atoms to alkylene oxide groups in alkoxylated alkyleneimine polymer (B) is at most 5.

Formulation according to one of claims 1 to 8, characterized in that it contains:

in the range of 1 to 50% by weight of aminocarboxylate (A),

total in the range of 0.001 to 2 wt .-% alkoxylated alkyleneimine polymer (B), based in each case on the solids content of the relevant formulation.

10. Use of formulations according to any one of claims 1 to 9 for rinsing dishes and kitchen utensils, wherein rinsing with water hardness of 2 to 25 ° dH. 1 1. Use of formulations according to any one of claims 1 to 9 for rinsing 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 the rinsing is a rinsing with a dishwasher.

13. Use according to one of claims 10 to 12, characterized in that one uses at least one formulation according to one of claims 1 to 8 for rinsing drinking glasses, glass vases and glass jars for cooking.

14. A process for the preparation of formulations according to any one of claims 1 to 9,

characterized in that one

(A) aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and (B) at least one alkoxylated alkyleneimine polymer having an average molecular weight Mw in the range from 800 to 25,000 g / mol which has a positive charge density of at least 5 meq / g and which is in the range from 2 to a maximum of 80% by weight of alkylene oxide side chains, based on the total alkoxylated alkyleneimine polymer,

and optionally further components in one or more steps mixed together in the presence of water and then the water is completely or partially removed.

15. The method according to claim 14, characterized in that the water is removed by spray drying or spray granulation.