EP2989192B1 - Formulations, use of same as or for manufacture of dish-washing agents and their manufacture - Google Patents

Description

1. (A) mindestens ein Aminocarboxylat, gewählt aus Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) und Glutaminsäurediacetat (GLDA) sowie deren Salzen, und
2. (B) mindestens ein alkoxyliertes Alkylenimin-Polymer mit einem mittleren Molekulargewicht M_w im Bereich von 500 bis unter 800 g/mol, das eine positive Ladungsdichte von mindestens 5 meq/g aufweist und das im Bereich von 2 bis maximal 80 Gew.-% Alkylenoxid-Seitenketten aufweist, bezogen auf gesamtes alkoxyliertes Alkylenimin-Polymer, wobei alkoxyliertes Alkylenimin-Polymer (B) auf Polyethylenimin mit einem mittleren Molekulargewicht M_w im Bereich von 400 bis 500 g/mol basiert, ermittelt durch Lichtstreuung.

The present invention relates to formulations containing

1. (A) at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and
2. (B) at least one alkoxylated alkyleneimine polymer having an average molecular weight M _w in the range of 500 to below 800 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 wt .-% Alkylene oxide side chains, based on total alkoxylated alkyleneimine polymer, wherein alkoxylated alkyleneimine polymer (B) based on polyethyleneimine having an average molecular weight M _w in the range of 400 to 500 g / mol, determined by light scattering.

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 rubbing glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences. For example, certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.

Glass corrosion has several effects. On the one hand, one can observe the formation of microscopically fine cracks, which are noticeable in the form of lines. On the other hand, 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 suggests formulations containing alkoxylated polyethylenimine for cleaning hard surfaces. For rinsing, purified water is used.

Out WO 2010/020765 Dishwashing agents are known which contain polyethyleneimine. Such dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion. Zinc and bismuth-containing dishwashing detergents are not recommended. 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.

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 solids content. Preferably, the formulation according to the invention has a heavy metal content below 0.05 ppm, based on the solids content of the relevant formulation.

In the context of the present invention, "heavy metals" are all metals having a specific density of at least 6 g / cm ³ . In particular, the heavy metals are precious metals and 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.

1. (A) mindestens ein Aminocarboxylat, gewählt aus Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) und Glutaminsäurediacetat (GLDA) sowie deren Salzen, im Rahmen der vorliegenden Erfindung kurz auch Aminocarboxylat (A) oder auch Verbindung (A) genannt, sowie vorzugsweise deren Salzen.

Contain formulations according to the invention

1. (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 briefly aminocarboxylate (A) or compound (A) mentioned, 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 counterions come, for example, inorganic Cations, for example ammonium, alkali or alkaline earth metal in question, preferably Mg ²⁺ , Ca ²⁺ , Na ⁺ , K ⁺ , or organic cations, preferably ammonium substituted with one or more organic radicals, in particular triethanolammonium, 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.

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 (GLDA).

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

• (B) mindestens ein alkoxyliertes Alkylenimin-Polymer mit einem mittleren Molekulargewicht M_w im Bereich von 500 bis unter 800 g/mol, bevorzugt 550 bis 750 g/mol, das eine positive Ladungsdichte von mindestens 5 meq/g aufweist und das im Bereich von 2 bis maximal 80 Gew.-%, bevorzugt 5 bis 60 Gew.-% Alkylenoxid-Seitenketten aufweist, bezogen auf gesamtes alkoxyliertes Alkylenimin-Polymer, wobei alkoxyliertes Alkylenimin-Polymer (B) auf Polyethylenimin mit einem mittleren Molekulargewicht M_w im Bereich von 400 bis 500 g/mol basiert, ermittelt durch Lichtstreuung.

Formulations according to the invention also contain

• (B) at least one alkoxylated alkyleneimine polymer having an average molecular weight M _w in the range of 500 to less than 800 g / mol, preferably 550 to 750 g / mol, which has a positive charge density of at least 5 meq / g and that in the range of 2 to a maximum of 80 wt .-%, preferably 5 to 60 wt .-% alkylene oxide side chains, based on total alkoxylated alkyleneimine polymer, wherein alkoxylated alkyleneimine polymer (B) on polyethyleneimine having an average molecular weight M _w in the range of 400th up to 500 g / mol, determined by light scattering.

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, polyalkylenepolyamines 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 in particular polyethyleneimine has an average molecular weight (M _w ) in the range of 400 to 500 g / mol, determined by light scattering.

Polyalkylenepolyamines can be covalently modified in partially quaternized (alkylated) form as the alkyleneimine 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 alkyleneimine polymer, the degree of quaternization (alkylation) is preferably 1 to 25, more 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 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 above-mentioned dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine. The aforementioned 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.

Ethyleneimine-grafted polyamidoamines 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.

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 one can use 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, with an indication in g of 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 wt .-%,
in each case based on solids content of the relevant formulation.

In a variant of the present invention, formulation according to the invention contains compound (A) and 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, wherein hydrogen phosphates are subsumed with, for example, free of trisodium phosphate, pentasodium tripolyphosphate and Hexasatriummetaphosphat. The term "free from" in connection with phosphates and polyphosphates in the context of the present invention should be understood to mean that the total content of phosphate and polyphosphate ranges from 10 ppm to 0.2% by weight, determined by gravimetry.

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 includes 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.

• (D) mindestens eine Verbindung, gewählt aus Alkalimetallpercarbonat, Alkalimetallperborat und Alkalimetallpersulfat, im Rahmen der vorliegenden Erfindung auch "Bleichmittel (D)" genannt.

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

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

Preferred bleaching agents (D) are selected from sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, and sodium persulfate, where the term "persulfate" respectively the salt of peracid H ₂ SO ₅ and the peroxodisulfate includes.

The alkali metal salts may each also be alkali metal hydrogencarbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulphate. However, preference is given in each case to the dialkali metal salts.

In one embodiment of the present invention formulation according to the invention contains zero to 50% by weight of sodium citrate (C), preferably 1 to 30% by weight, more 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 tableting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizing agents.

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

in der die Variablen wie folgt definiert sind:

R¹

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

R²

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

R³

gewählt aus C₁-C₁₀-Alkyl, Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl oder iso-Decyl,

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

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

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

R ³

selected from C ₁ -C ₁₀ -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl,

m and n are in the range of zero to 300, where the sum of n and m is at least one. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

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

in der die Variablen wie folgt definiert sind:

R¹

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

R⁴

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

a

eine Zahl im Bereich von 1 bis 6,

b

ist eine Zahl im Bereich von 4 bis 20,

d

ist eine Zahl im Bereich von 4 bis 25.

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

where the variables are defined as follows:

R ¹

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 ⁴

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

a

a number in the range of 1 to 6,

b

is a number in the range of 4 to 20,

d

is a number in the range of 4 to 25.

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

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

It may also contain mixtures of several different nonionic surfactants.

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

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

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

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

Formulations according to the invention may comprise, in addition to sodium citrate (C), 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 α-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ , and δ-Na ₂ Si ₂ O ₅ , furthermore 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 are selected, for example, alkali metal salts of (meth) acrylic acid homo- or (meth) acrylic acid copolymers.

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

It is also possible to use copolymers of at least one monomer selected from the group consisting of monoethylenically unsaturated C ₃ -C ₁₀ -mono- or 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 one hydrophilic or hydrophobically modified monomers are used as listed 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, C ₂₂ -α-olefin, a mixture of C ₂₀ -C ₂₄ -α-olefins and polyisobutene with 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 co-builders are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.

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 and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.

Formulations according to the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxo-hexahydroxy 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.

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

Glass surface may be decorated, for example colored or printed, or not decorated.

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

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

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

In one embodiment of the present invention, water having a hardness in the range from 1 to 30 ° dH, preferably from 2 to 25 ° dH, is used for cleaning, German hardness being taken to mean in particular the calcium hardness.

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 of the present invention to clean glass together with metal objects, such as pots, pans or garlic presses.

Furthermore, it can be observed that formulations according to the invention have a very good bleaching action when used for rinsing dishes and kitchen utensils and glass surfaces.

1. (A) Aminocarboxylat, gewählt aus Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) und Glutaminsäurediacetat (GLDA) sowie deren Salzen, und
2. (B) mindestens ein alkoxyliertes Alkylenimin-Polymer mit einem mittleren Molekulargewicht M_w im Bereich von 500 bis unter 800 g/mol, das eine positive Ladungsdichte von mindestens 5 meq/g aufweist und in dem im Bereich von 2 bis maximal 80 Gew.-% Alkylenoxid-Seitenketten aufweist, bezogen auf gesamtes alkoxyliertes Alkylenimin-Polymer, wobei alkoxyliertes Alkylenimin-Polymer (B) auf Polyethylenimin mit einem mittleren Molekulargewicht M_w im Bereich von 400 bis 500 g/mol basiert, ermittelt durch Lichtstreuung,
   und gegebenenfalls
3. (C) Natriumcitrat oder
4. (D) mindestens eine Verbindung, gewählt aus Alkalimetallpercarbonat, Alkalimetallperborat und Alkalimetallpersulfat,

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

1. (A) aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and
2. (B) at least one alkoxylated alkyleneimine polymer having an average molecular weight M _w in the range from 500 to less than 800 g / mol, which has a positive charge density of at least 5 meq / g and in which in the range from 2 to a maximum of 80 wt. % Alkylene oxide side chains, based on the total alkoxylated alkyleneimine polymer, wherein alkoxylated alkyleneimine polymer (B) is based on polyethyleneimine having an average molecular weight M _w in the range from 400 to 500 g / mol, determined by light scattering,
   and optionally
3. (C) sodium citrate or
4. (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 a plurality of 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 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 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 can be tested as follows.

General: Care must be 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

• LA: Ladungsdichte des betreffenden modifizierten Polyethylenimins (B), meq/g (Milliäquivalent/g)
• KV: Verbrauch der N/400-KPVS-Lösung [ml]

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. With a buffer solution and aqueous HCl was set to a pH of 4.0, determined potentiometrically. Three ml of an aqueous solution of toluidine blue (50 mg / l water) was added and titrated N / 400-KPVS (potassium polyvinyl sulfate) solution (Wako) with a concentration of 0.0004 meq / ml to a color change of blue pink. The charge density was calculated as follows: $$\mathrm{LA}=0.4\cdot \mathrm{KV}$$

• LA: charge density of the respective modified polyethyleneimine (B), meq / g (milliequivalent / g)
• KV: consumption of N / 400 KPVS solution [ml]

I.1 Preparation of basic mixtures

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

Abbreviations:

• MGDA: methylglycine diacetic acid as trisodium salt
• TAED: N, N, N ', N'-tetraacetylethylenediamine

Action:

In a 100 ml beaker, add 20 ml of distilled water and add modified polyethylenimine (B).

Then stir for 10 minutes. Then, MGDA trisodium salt (A.1) dissolved in 30 ml of water is added according to Table 3. Then add basic mixture, stir again and evaporate the water.

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 is carried out as follows. II.1 Test method Dishwasher with endurance runner Dishwasher: Miele G 1222 SCL Program: 65 ° C (with pre-rinse) ware: 3 champagne glasses "GILDE", 3 shot glasses, "INTERMEZZO"

For cleaning, the glasses are arranged in the upper dish rack of the dishwasher. The dishwashing agent used is in each case 25 g of formulation according to the invention or 25 g of comparative formulation. Rinse at a rinse temperature of 55 ° C. The water hardness is in each case in the range of zero to 2 ° dH. One flushes every 100 rinse cycles, i.e., the program is run 100 times. The evaluation is carried out gravimetrically and visually after 100 rinsing cycles.

The weight of the glasses is 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 items to be cleaned is 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 are awarded.

Experimental procedure:

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

To assess the gravimetric removal, the dry test specimens are weighed. This is followed by the visual assessment of the test specimens. Here, the surface of the test specimens is evaluated for line corrosion (scorching) and haze corrosion (areal haze).

The assessments are 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

• T5: no haze visible
• T4: low turbidity in very few areas
• T3: cloudiness in some areas
• T2: turbidity in several areas
• T1: markedly turbid over almost the entire glass surface

Interim scores (eg L3-4) were also allowed for the match. II.1 Test method Dishwasher with endurance runner Dishwasher: Miele G 1222 SCL Program: 65 ° C (with pre-rinse) 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 inventive formulation individually specified. Rinsing was carried out at a rinse temperature of 55 ° C. The water hardness was in each case in the range of zero to 2 ° dH. One rinsed 100 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, for the purpose of pretreatment, the specimens were rinsed in a domestic dishwasher (Bosch SGS5602) with 1 g of surfactant (nC ₁₈ F ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH) and 20 g of citric acid to remove any impurities. The test pieces were dried, their weight determined and fixed on the grid floor insert.

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

The assessments were made according to the following scheme.

Line corrosion:

• L5: no lines to recognize
• L4: in very few areas low line formation, fine line corrosion
• L3: line corrosion in some areas
• L2: line corrosion in several areas
• L1: Strong line corrosion

glass opacity

• L5: no haze visible
• L4: low turbidity in very few areas
• L3: cloudiness in some areas
• L2: cloudiness in several areas
• L1: markedly turbid over almost the entire glass surface

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

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

II.3 Results

The results are summarized in Table 3. Table 3: Results of tests with dishwasher (endurance runner) Example no. Base mixture: [g] (A.1) [g] (B) [mg] Weight loss champagne glass [mg] Weight loss shot glass [mg] Visual rating champagne glass Visual rating shot glass V-1 Base 2:17 3 --- 80 48 L1, T1-2 L1, T1-2 1 Base 2:17 3 60 (B.1.1.1) 17 9 L4, T4-5 L4, T5 2 Base 2:17 3 30 (B.1.1.1) 19 11 L3-4, T4-5 L4, T5 V-3 Base 2:17 3 30 (B.1.1.3) 67 36 L2, T2 L1-2, T2-3 V-4 Base 2:17 3 25 (B.2.2.3) 69 39 L2-3, T2 L2, T2

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

Claims (15)

1. A formulation which is free from heavy metals, comprising

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

   (B) at least one alkoxylated alkyleneimine polymer with an average molecular weight M_w in the range from 500 to below 800 g/mol which has a positive charge density of at least 5 meq/g and which has in the range from 2 to at most 80% by weight alkylene oxide side chains, based on total alkoxylated alkyleneimine polymer, where alkoxylated alkyleneimine polymer (B) is based on polyethyleneimine with an average molecular weight M_w in the range from 400 to 500 g/mol, ascertained by light scattering.
2. The formulation according to claim 1, which is free from phosphates and polyphosphates.
3. The formulation according to claim 1 or 2, wherein (B) is selected from polyethyleneimines which have been reacted with ethylene oxide or propylene oxide.
4. The formulation according to any one of claims 1 to 3, which has a heavy metal content below 0.05 ppm, based on the solids content of the formulation in question.
5. The formulation according to any one of claims 1 to 4, wherein alkyleneimine polymer (B) is selected from those in which at most 30 mol% of the nitrogen atoms of the alkyleneimine polymer have been reacted with propylene oxide.
6. The formulation according to any one of claims 1 to 5, which is solid at room temperature.
7. The formulation according to any one of claims 1 to 6, which comprises in the range from 0.1 to 10% by weight of water.
8. The formulation according to any one of claims 1 to 7, wherein the molar ratio of nitrogen atoms to alkylene oxide groups in the alkoxylated alkyleneimine polymer (B) is at most 5.
9. The formulation according to any one of claims 1 to 8, which comprises:

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

   in total in the range fro 0.001 to 2% by weight of alkoxylated alkyleneimine polymer (B),

   based in each case on the solids content of the formulation in question.
10. The use of formulations according to any one of claims 1 to 9 for washing dishes and kitchen utensils, where washing is carried out with water of hardness from 2 to 25° German hardness.
11. The use of formulations according to any one of claims 1 to 9 for washing objects which have at least one surface made of glass, which may be decorated or undecorated.
12. The use according to claim 10 or 11, wherein the washing is washing using a dishwasher.
13. The use according to any one of claims 10 to 12, wherein at least one formulation according to any one of claims 1 to 8 is used for washing drinking glasses, glass vases and glass vessels for cooking.
14. A process for producing formulations according to any one of claims 1 to 9, wherein

    (A) aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof, and

    (B) at least one alkoxylated alkyleneimine polymer with an average molecular weight M_w in the range from 500 to below 800 g/mol which has a positive charge density of at least 5 meq/g and which has in the range from 2 to at most 80% by weight alkylene oxide side chains, based on total alkoxylated alkyleneimine polymer,

    and optionally further components are mixed in one or more steps with one another in the presence of water and then the water is completely or partially removed.
15. The process according to claim 14, wherein the water is removed by spray-drying or spray-granulation.