MX2014013009A - Formulations, use thereof as or for production of dishwashing detergents and production thereof. - Google Patents

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 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 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, ITS USE AS OR TO PRODUCE DETERGENTS DISHWASHER AND ITS PRODUCTION The present invention relates to formulations comprising (A) at least one 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 Mw in the range of 800 to 25,000 g / lol having a positive charge density of at least 5 meq / g and having in the range of 2 a, at most, 80% by weight of alkylene oxide side chains, based on total alkoxylated alkyleneimine polymer.

On the other hand, the present invention relates to a process for producing formulations according to the invention and to their use as or to produce dishwashing detergents, in particular dishwashing detergents for dishwashing machines.

Detergent dishwashers must meet many requirements. For example, they should clean the dishes thoroughly, they should not have harmful or potentially harmful substances in the wastewater, they should allow the draining and drying of the water in the dishes and should not cause problems during the operation of the dishwasher. Finally, they should not produce aesthetically undesirable results in the article to be cleaned. In this regard, the corrosion of the glass should be mentioned in particular.

Glass corrosion arises not only as a result of mechanical effects, for example, as a result of crystals rubbing against each other or mechanical contact between the glass and parts of the dishwasher, but is primarily promoted by chemical influences. For example, certain ions can be dissolved from the glass as a result of repeated machine cleaning, which adversely alters the optical properties and, thus, the aesthetic properties.

Several effects are observed with the corrosion of the crystals. First, the formation of microscopically thin cracks can be observed, which become noticeable in the form of lines. Secondly, in many cases, a general turbidity can be observed, for example, a roughness, which makes the glass in question not look attractive. Effects of this type are also generally subdivided into iridescent discoloration, scraping, as well as irregular and circular opacity.

WO 2006/108857 discloses alkoxylated polyethyleneimines as additives for detergents. By way of example, detergents comprising zeolites or polyaminocarboxylates such as EDTA or triethylene diamine pentaacetate as complexing agents are disclosed.

WO 01/96516 proposes formulations comprising alkoxylated polyethyleneimine for cleaning hard surfaces. The purified water is used for rinsing.

WO 2010/020765 discloses dishwashing detergents comprising polyethylene imine. Dishwashing detergents of this type they can comprise phosphate or they can be free of phosphate. They are credited with good inhibition of crystal corrosion. Dishwashing detergents containing zinc and bismuth are discouraged. The corrosion of the glass, in particular the corrosion of lines and scraping, however, in many cases, is not delayed or avoided in an appropriate manner.

Accordingly, it was the object to provide formulations which were suitable as or to produce dishwashing detergents and which avoided the known disadvantages of the prior art and inhibited glass corrosion or at least reduced it particularly well. It was also intended to provide a process for producing formulations that are suitable as or to produce dishwashing detergents and which avoid the known disadvantages of the prior art. It was also intended to provide uses of formulations.

Accordingly, the formulations defined at the beginning, also abbreviated as formulations according to the invention, were found.

The formulations according to the invention are free of heavy metals. Within the context of the present invention, it is to be understood that the formulations according to the invention are free of those heavy metal compounds which do not act as bleaching catalysts, in particular iron and bismuth compounds. In connection with heavy metal compounds, within the context of the present invention, "free of" is to be understood as meaning that the content of heavy metal compounds that do not act as bleaching catalysts is in total in the range of 0 to 100 ppm , determined by the Leach method and based on the content of solid Preferably, the formulation according to the invention has a heavy metal content of less than 0.05 ppm, based on the solids content of the formulation in question.

Within the context 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 precious metals and also zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.

Preferably, the formulation according to the invention does not comprise measurable fractions of zinc and bismuth compounds, i.e., for example, less than 1 ppm.

The formulations according to the invention comprise (A) at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA) and salts thereof, within the context of the present invention also referred to as abbreviating aminocarboxylate (A) or even compound (A) and preferably salts thereof.

Preferably, the compound (A) is selected as the free acid, with particular preference, in partially or completely neutralized form, that is, as a salt. Suitable counterions are, for example, inorganic cations, for example ammonium, alkali metal or alkaline earth metal, preferably, cations g2 +, Ca2 +, Na +, K + or organic, preferably, ammonium substituted with one or more organic radicals, in particular triethanolammonium, N, N-diethanolammonium, N-mono- C 1 -C 4 alkyl diethanolammonium, for example, N-methyldiethanolammonium or N-n-butyldiethanolammonium and N, N-di-alkyl C -C 4 -ethanolammonium.

Particularly preferred compounds (A) are alkali metal salts, in particular the sodium salts of methylglycine diacetate (MGDA), iminosuccinic acid (IDA) and glutamic acid diacetate (GLDA).

With particular preference, methylglycine diacetate (MGDA), the iminosuccinic acid (IDA) or the glutamic acid diacetate (GLDA) is completely neutralized.

On the other hand, formulations according to the invention comprise (B) at least one alkoxylated alkyleneimine polymer with an average molecular weight Mw in the range of 800 to 25,000 g / mol having a positive charge density of at least 5 meq / g and having in the range of 2 a, at most 80% by weight, preferably 5 to 60% by weight, of alkylene oxide side chains, based on total alkoxylated alkyleneimine polymer.

Within the context of the present invention, modified alkyleneimine polymers of this type are also referred to as modified polyalkyleneimine (B) for short.

Within the context of the present invention, alkyleneimine polymers are to be understood as 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 mine. Examples are polyalkylene polyamines and grafted polyimidoamines with ethyleneimine.

Within the context of the present invention, polyalkylenepolyamines are preferably understood as those polymers comprising at least 6 nitrogen atoms and at least five C2-Ci0 alkylene units, preferably C2-C3 alkylene units, per molecule, for example, pentaethylenehexamine and in particular polyethyleneimines.

The alkyleneimine polymer and in particular the polyethylenimine can have, for example, an average molecular weight (Mw) of at least 300 g / mol; Preferably, the average molecular weight of polyethyleneimine is in the range of 800 to 20,000 g / mol, confirmed by light diffraction.

The polyalkylene polyamines 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-C alkyl chloride, such as methyl chloride, methyl bromide., methyl iodide, ethyl chloride, ethyl bromide, n-butyl chloride, tert-butyl chloride, n-hexyl chloride, also epichlorohydrin, d i methyl sulfate, diethyl isulfate and benzyl chloride. If the quaternized (alkylated) polyalkylenepolyamines as the alkyleneimine polymer are covalently modified, the degree of quaternization (alkylation) is preferably from 1 to 25, with particular preference, up to 20% by moles, based on N atoms. quaternizable (alkylatable) in an alkyleneimine polymer.

On the other hand, polyamidoamines grafted with ethyleneimine are suitable as alkyleneimine polymers. Suitable polyamidoamines can be obtained, for example, by reacting C4-C10 dicarboxylic acids with polyalkylene polyamines, preferably comprising from 3 to 10 basic nitrogen atoms in the molecule. Suitable dicarboxylic acids are, for example, succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is also possible to use mixtures of the aforementioned dicarboxylic acids, for example mixtures of adipic acid and glutaric acid or mixtures of maleic acid and adipic acid. Preference is given to the use of adipic acid to produce polyamidoamines. Suitable polyalkylenepolyamines which were condensed with the aforementioned dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bis-aminopropylethylenediamine. The aforementioned polyalkylene polyamines can also be used in the form of mixtures in the production of polyamidoamine. The production of polyamidoamine preferably takes place without dilution, but it can also be carried out optionally in inert solvents. The condensation of dicarboxylic acid with polyalkylene polyamine takes place at elevated temperatures, for example, in the range of 120 to 220 ° C. The water formed during the reaction is distilled from the reaction mixture. The condensation can optionally be carried out in the presence of lactones or lactams of carboxylic acids having 4 to 8 carbon atoms. carbon. In general, 0.8 to 1.4 moles of polyalkylene polyamine are used per mole of dicarboxylic acid. The polyamidoamines obtainable in this way have primary and secondary NH groups and are soluble in water.

The polyamidoamines grafted with ethyleneimine can be prepared by allowing the ethyleneimine to act on the polyamidoamine described above in the presence of Bronstedt acids or Lewis acids, for example, sulfuric acid, phosphoric acid or boron trifluoride etherate. As a result, ethyleneimine is grafted onto the polyamidoamine in question. For example, 1 to 10 ethylene imine units can be grafted per basic nitrogen atom into the polyamidoamine, ie, about 10 to 500 parts by weight of ethyleneimine per 100 parts by weight of polyamidoamine are used.

A preferred alkyleneimine polymer is polyethylene imine.

In one embodiment of the present invention, the polyethylene imines are selected from highly branched polyethylene imines. The highly branched polyethyleneimines 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 20 and is defined as follows: DB = D + T / D + T + L with D (dendritic) corresponding to the fraction of tertiary amino groups, L (linear) corresponding to the fraction of the secondary amino groups and T (terminal) corresponding to the fraction of the primary amino groups.

Within the context of the present invention, polyethyleneimines highly branched polyethyleneimines with DB in the range of 0.1 to 0.95, preferably 0.25 to 0.90, with particular preference in the range of 0.30 to 0.80 and with particular preference , of at least 0.5.

In one embodiment of the present invention, polyethyleneimine are highly branched polyethyleneimines (homopolymers) with an average molecular weight Mw in the range of 600 to 20,000 g / mol, preferably in the range of 800 to 15,000 g / mol. mol.

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

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

In one embodiment of the present invention, the modified alkyleneimine (B) is selected from polyethylene imines that were reacted with ethylene oxides or propylene oxides.

The modified polyalkyleneimine (B) can have, as counterions, high molecular weight or low molecular weight anions, organic or, preferably, inorganic. Within the context of the present invention, high molecular weight anions 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 organic low molecular weight counterions are acetate, propionate and benzoate. Examples of low molecular weight inorganic counter ions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate and hydrogen carbonate.

In one embodiment of the present invention, the modified polyalkyleneimine (B) has a cationic charge density of at least 5 meq / g up to at most 25 meq / g (milliequivalents / g), preferably up to 22 meq / g. g, where the data in g refer to the modified polyalkyleneimine (B) without taking into account the counterions. The cationic charge density can be confirmed, for example, by titration, for example, with polyvinyl sulfate solution.

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

In an embodiment of the present invention, the formulations according to the invention comprise in total in the range from 1 to 50% by weight of aminocarboxylate (A), preferably from 10 to 25% by weight, in total in the range of 0.001 to 5% by weight of polyalkyleneimine modified (B), preferably from 0.02 to 0.5% by weight, based in each case on the solids content of the formulation in question.

In a variant of the present invention, the formulation according to the invention comprises the compound (A) and the modified polyalkyleneimine (B) in a weight ratio in the range of 1000: 1 to 25: 1.

In a preferred embodiment of the present invention, the formulation according to the invention is free of phosphates and polyphosphates, the hydrogen phosphates also being subsumed, for example, free of trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate in connection with phosphates. and polyphosphates, within the context of the present invention, "free of" is to be understood as the content of phosphate and polyphosphate in total is in the range of 10 ppm to 0.2% by weight, determined by gravimetry.

The formulations according to the invention may comprise other components which are advantageous, for example, for use when washing dishes and / or kitchen utensils.

In another embodiment of the present invention, the formulations according to the invention do not comprise other components which are advantageous, for example, for use when washing dishes and / or kitchen utensils, but can be easily formulated with other components and, consequently, they are appropriate as starting material.

In an embodiment of the present invention, the formulations according to the invention comprise sodium citrate (C) In this sense, the expression sodium citrate includes the monosodium salt and, preferably, the disodium salt. Sodium citrate can be used as an anhydrous salt or as a hydrate, for example, as a dihydrate.

In an embodiment of the present invention, the formulations according to the invention comprise (D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, within the context of the present invention also referred to as "bleach (D)".

Preferred bleaches (D) are selected from sodium perborate, anhydrous or, for example, as monohydrate or as a tetrahydrate or the so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate and sodium persulfate, the term " persulfate "in each case including the peracid salt H2S05 and also the peroxodisulfate.

In this sense, the alkali metal salts can also in each case be alkali metal hydrogen carbonate, alkali metal hydrogen perborate and alkali metal hydrogen-persulfate. However, preference is given in each case to the dialkyl metal salts.

In an embodiment of the present invention, the formulation according to the invention comprises 0 to 50% by weight of sodium citrate (C), preferably 1 to 30% by weight, with particular preference, at least 5% by weight. % by weight of sodium citrate (C), determined as anhydrous sodium citrate, in total 0 to 15% by weight of bleach (D), preferably, at least 0.5% by weight of bleach (D) selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, at each case based on the solids content of the formulation in question.

In one embodiment of the present invention, the formulation according to the invention is solid at room temperature, for example, a powder or a tablet. In another embodiment of the present invention, the formulation according to the invention is liquid at room temperature. In an embodiment of the present invention, the formulation according to the invention are granules, a liquid preparation or a gel.

In an embodiment of the present invention, the formulation according to the invention comprises 0.1 to 10% by weight of water, based on the sum of all the solids of the formulation in question.

In one embodiment of the present invention, the formulation according to the invention may have other ingredients (E), for example, one or more surfactants, one or more enzymes, one or more formers, in particular phosphorus-free formers, one or several coformers, one or more alkaline 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, or several forming substances, buffers, dyes, one or several fragrances, one or more organic solvents, one or more tableting aids, one or more disintegrants, one or more thickeners or one or more solubility promoters.

Examples of surfactants are in particular nonionic surfactants and also 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 oxides and propylene oxides and reaction products of sorbitan with ethylene oxides or propylene oxides, alkyl glucosides and the so-called oxides of amine.

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I) (I) where the variables are defined as follows: R1 is identical or different and is selected from linear C1-C10 alkyl, preferably, in each case identical and ethyl and with particular preference, methyl, R2 is selected from C8-C22 alkyl, for example, n-C8H17, n-C10H21, n-Ci2H25, n- Ci4H29, n-C16H33 or n- CI8H37, R3 is selected from Ci-C10 alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. -butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1, 2-dimethylpropyl, isoamyl, n- hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl, m and n are in the range of 0 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.

Here, the compounds of the general formula (I) may be block copolymers or random copolymers, giving preference to the 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: R1 is identical or different and is selected from linear alkyl CT-C-IO, preferably, in each case identical and ethyl and with particular preference, methyl, R4 is selected from C6-C2o alkyl, in particular n-C8H7, n-C10H21, n-Ci2H25, n-C14H29, n-C16H33, n- CieH37, 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.

Here, the compounds of the general formula (II) may be block copolymers or random copolymers, giving preference to the block copolymers.

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

Two or more different nonionic surfactants may also be present.

Examples of anionic surfactants are C8-C2o alkyl sulfates, C8-C20 alkyl sulfonates and C8-C20 alkyl ether sulphates with 1 to 6 units of ethylene oxides per molecule.

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

The formulations according to the invention may comprise one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.

The formulations according to the invention may comprise, for example, up to 5% by weight of enzyme, with preference given to 0.1 to 3% by weight, in each case, based on the total solids content of the formulation according to the invention. with the invention In addition to sodium citrate (C), the formulations in accordance with The invention may comprise one or more formers, in particular phosphate-free formers. Examples of suitable formers are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, layered silicates, in particular those of the formula a-Na2Si205, p-Na2Si205 and o-Na2Si205, also sulfonates of fatty acids, hydroxypropionic, alkali metal malonate, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch and polymeric formers, for example, polycarboxylates and polyaspartic acid.

In one embodiment of the present invention, the formers are selected from polycarboxylates, for example, alkali metal salts of homopolymers of (meth) acrylic acid or copolymers of (meth) acrylic acid.

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 Mw in the range of 2000 to 40 000 g / mol, preferably 2000 to 10 000 g / mol, in particular 3000 to 8000 g / mol . Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.

It is also possible to use copolymers of at least one monomer of the group consisting of C3-C10 monocarboxylic acids or acids C4-C10 monoethylenically unsaturated dicarboxylics or their drides, such as maleic acid, maleic dride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, with at least one hydrophilic or hydrophobically modified monomer, 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, such as, for example, 1-decene, 1-dodecene, 1- tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docoseno, 1-tetracoseno and 1-hexacoseno, to-olefin C22, a mixture of a-olefinas C20-C24 and poliisobuteno that has, in average, 12 to 100 carbon atoms per molecule.

Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups and also non-ionic monomers with hydroxyl function or alkylene oxide groups. By way of example, mention may be made of: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (metha) acrylate, methoxypolibutylene glycol (metha) acrylate, methoxypoly (metha) acrylate (propylene-co-oxides) ethylene oxides), ethoxy polyethylene glycol (metha) acrylate, ethoxy polypropylene glycol (metha) acrylate, ethoxy polyethylene glycol (metha) acrylate and ethoxy poly (methylene acrylate) (propylene oxides-co-ethylene oxides). The polyalkylene glycols herein can comprise 3 to 50, in particular 5 to 40 and in particular 10 to 30 units of alkylene oxide per molecule.

Monomers of particular preference which contain groups of sulfonic acid here are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2 acid -hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methanoxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulphonic acid, acrylate 3-sulfopropyl, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and salts of said acids, such as their sodium, potassium or ammonium salts.

Monomers of particular preference which contain phosphonate groups are vinylphosphonic acid and its salts.

Moreover, amphoteric polymers can also be used as formers.

The formulations according to the invention may comprise, for example, in the total range of 10 to 50% by weight, preferably up to 20% by weight of formers.

In an embodiment of the present invention, the formulations according to the invention may comprise one or more coforms.

Examples of coforms are phosphonates, for example, hydroxyalkanephosphonates and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a coformer. It can be used, with Preferably, as the sodium salt, the disodium salt gives a neutral reaction and the tetrasodium salt gives an alkaline reaction (pH 9). Suitable aminoalkanphosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Are used, preferably in the form of sodium salts of neutral reaction, for example as the hexasodium salt of EDTMP or as the hepta- and octasódicas salts of DTPMP.

The formulations according to the invention can comprise one or more alkaline carriers. Alkaline carriers ensure, for example, a pH of at least 9, if an alkaline pH is desired. Suitable are, for example, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides and alkali metal metasilicates. A preferred alkali metal is, in each case, potassium, with particular preference given to sodium.

In addition to the bleaches (D), the formulations according to the invention may comprise one or more chlorine-containing bleaches.

Suitable chlorine bleaches 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.

The formulations according to the invention may comprise, for example, in the range from 3 to 10% by weight of bleach with chlorine content.

The formulations according to the invention may comprise one or more bleach catalysts. Bleaching catalysts may be selected from transition metal salts that enhance bleaching or complexes of transition metals such as, for example, complexes of manganese, iron, cobalt, ruthenium or molybdenum or carbonyl salts. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes can also be used with three-foot ligands containing nitrogen and also complexes of cobalt-, iron-, copper- and ruthenium-amine as bleach catalysts.

The formulations according to the invention may comprise one or more whitening activators, for example, N-methylmorpholinium-acetonitrile salts ("MMA salts"), trimethylammonioacetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1, 5-diacetyl-2,2-dioxohexahydro-1, 3,5-triazine ("DADHT") or nitrile quats (trimethylammonium acetonitrile salts).

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

The formulations according to the invention may comprise one or more corrosion inhibitors. In the present case, it should be understood as including those compounds that inhibit the corrosion of the metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, phenolic derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

In one embodiment of the present invention, the formulations according to the invention comprise in total in the range from 0.1 to 1.5% by weight of corrosion inhibitor.

The formulations according to the invention may comprise one or more forming substances, for example, sodium sulfate.

The formulations according to the invention may comprise one or more defoamers, selected, for example, from silicone oils and paraffin oils.

In an embodiment of the present invention, the formulations according to the invention comprise in total in the range of 0.05 to 0.5% by weight of antifoam.

The formulations according to the invention may comprise phosphonic acid or one or more phosphonic acid derivatives, for example, hydroxyethane-1,1-diphosphonic acid.

The present invention also provides the use of formulations according to the invention for cleaning tableware and kitchen utensils. Within the scope of the present invention, the kitchen utensils that may be mentioned are, for example, pots, pans, pans, and also objects made of metal such as, for example, slotted spoons, fish slices and garlic presses.

Preference is given to the use of formulations according to invention for machine cleaning of objects having at least one surface made of glass, which may be decorated or not decorated. In this regard, within the context of the present invention, a surface made of glass is to be understood as having the object in question having at least one section made of glass that comes in contact with the ambient air and can become dirty after using the object. Thus, the objects in question can be those that, like glasses or bowls, are made essentially of glass. However, they can also be, for example, lids having individual components made of a different material, for example, lids of pots with edges and handle made of metal.

The surfaces made of glass may be decorated, for example, colored or printed or may not be decorated.

The term "crystal" includes any type of desired glass, for example, lead glass and in particular soda-lime glass, glass glass and borosilicate glass.

Preferably, machine cleaning is washed with a dishwasher (automatic dishwasher).

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

In an embodiment of the present invention, for cleaning, water with a hardness in the range of 1 to 30 ° of Germán hardness is used, preferably 2 to 25 ° of Germán hardness, where Germán hardness it is to be understood in particular as the hardness of the calcium.

Also for rinsing, it is also possible to use water with a hardness in the range of 1 to 30 ° of Germán hardness, preferably from 2 to 25 ° of Germán hardness.

If formulations according to the invention are used for machine cleaning, then, even in the case of repeated machine cleaning of objects having at least one surface made of glass, only a very slight tendency towards corrosion of the glass is observed. and then only if objects that have at least one surface made of glass are cleaned together with very dirty cutlery or crockery. Moreover, it is significantly less harmful to use the formulation according to the invention to clean glass together with objects made of metal, for example, together with pots, pans or garlic presses.

On the other hand, it can be seen that the formulations according to the invention have a bleaching effect of products when they are used to wash dishes and kitchen utensils and glass surfaces.

The present invention also provides a process for the production of formulations according to the invention, also abbreviated as a production process according to the invention. To carry out the production process according to the invention, the process can be, for example, that which mixes (A) aminocarboxylate selected from methylglycine diacetate.

(MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA) and salts thereof, and (B) at least one alkoxylated alkylenelamine polymer with an average molecular weight Mw in the range of 800 to 25,000 g / mol having a positive charge density of at least 5 meq / g and having in the range of 2 a, at most, 80% by weight, of alkylene oxide side chains, based on 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 other components (E) in one or several stages in the presence of water and then the water is completely or partially removed.

The compound (A), the modified polyalkyleneimine (B) and the bleach (D) are defined above.

In an embodiment of the present invention, before at least partially removing the water, mixing with one or more other ingredients (E) for formulation according to the invention is possible, for example, with one or more surfactants, one or several enzymes, one or more formers, one or more coforms, in particular phosphorus-free formers, one or more alkaline carriers, one or more bleaching agents, one or more bleaching catalysts, one or more bleach activators, one or more bleach stabilizers , one or more defoamers, one or more corrosion inhibitors, one or more forming substances, with buffer or dyeing.

In one embodiment, the method involves removing the water of the formulation according to the invention wholly or in part, for example, up to a residual moisture in the range of 0.1 to 10% by weight, evaporating it, in particular by means of of spray drying, spray granulation or compaction.

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

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

By means of the production process according to the invention, formulations according to the invention can be easily obtained.

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

The invention is illustrated by means of working examples.

General: it was ensured that, after the first cleaning of the test bodies in the domestic dishwasher until after the weighing and visual inspection of the crystals, the test bodies They were only handled with clean cotton gloves, so that the weight and / or visual impression of the bodies was not falsified.

The data in% is% by weight, unless otherwise expressly stated.

I. Preparation of formulations according to the invention The charge density of modified polyethyleneimines (B) was always determined in the following manner (see also: Horn, Prog. Colloid &Polym, Sci. 1978, 65, 251): 1 g of the modified polyethyleneimide (B) in question was dissolved in 100 ml of demineralized water. A buffer solution and aqueous HCl were used to establish a pH of 4.0, it was determined potentiometrically. Three ml of an aqueous solution of toluidine blue (50 mg / l of water) were added and the solution of N / 400-KPVS (potassium polyvinylsulfate) (Wako) at a concentration of 0.0004 meq / ml was titrated until the color changed from blue to pink. The charge density was calculated as follows: LA = 0.4 · KV LA: the charge density of the modified polyethyleneimine (B) in question, meq / g (milliequivalent / g) KV: consumption of the solution of N / 400-KPVS, mi 1. 1 Preparation of base mixtures First, the base mixtures were prepared from the feedstocks according to table 1. The materials of feed were mixed dry.

Table 1: mixtures of bases for experiments with formulations according to the invention and comparative formulations All the data in g.

Abbreviations: MGDA: methylglycliciacetic acid as trisodium salt TAED: N, N, N ', N'-Tetraacetylethylenediamine I.2 Preparation of formulations according to the invention 1. 2.1 Preparation of formulations 2 to 8 according to the invention and comparison of formulations V1 Modified polyethyleneimines (B) were used according to table 2 which had been prepared according to the following general procedure: Polyethyleneimine was introduced according to Table 2, columns 2 and 3 and pellets at 0.7% by weight of KOH (water content of 50% by weight, KOH residue), based on polyethyleneimine, in a 2-liter autoclave. . The mixture was heated to 120 ° C under reduced pressure (10 mbar) and it was stirred for 2 hours at 120 ° C, during which the water was removed. The autoclave was then flooded three times with nitrogen and then heated to 140 ° C with an initial pressure of 1 bar. Then, during a 2 hour period, ethylene oxides or propylene oxides were added according to table 2, column 5. After the addition was complete, the mixture was stirred for another 3 hours at 140 ° C. Then, the water or optionally other volatile compounds were removed under reduced pressure (10 mbar) at 90 ° C. This gave modified polyethyleneimines (B) according to the table in the form of pale yellow wax-like solids.

Table 2: Modified polyethyleneimines (B) Abbreviations in table 2: AO: alkylene oxide Column 2: Mw PEI refers to the molecular weight of the polyethyleneimine used for the alkoxylation, ie, unmodified polyethylenimine. Column 3: PEI refers to unmodified polyethyleneimine.

Column 7: the molar fractions refer to the starting substances.

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

Process: 20 ml of distilled water were placed in a 100 ml spout container and modified polyethylenimine (B) was added according to tables 2 and 3 with stirring.

The stirring was then carried out for 10 minutes. Then, trisodium salt of MGDA (A.1), dissolved in 30 ml of water, was added according to table 3. This gave a clearly transparent solution. The mixture of bases according to Table 3 was then added, the mixture was again stirred and the water evaporated.

If in the trial the corresponding fractions of mixture of bases are dosed separately from the aqueous solution of (A.1), (B), (C.1) or (D.1), the same results are obtained when the dry formulation was tested with identical amounts of active ingredient. The order of the dosed addition, therefore, has no consequences.

II. Use of formulations according to the invention and comparative formulations for cleaning glassware General: it was ensured that, after the first cleaning of the test bodies in the domestic dishwasher until after the weighing and visual inspection of the vessels, the test bodies were handled only with clean cotton gloves so that the weight and / or the visual impression of the test bodies will not be falsified.

The testing of formulations according to the invention and comparative formulations was carried out in the following manner. 11. 1 Test method for dishwashers with continuous operation Dishwasher: Miele G 1222 SCL Program: 65 ° C (with prewash) Crockery: 3 glasses of champagne "GILDE", 3 glasses of brandy "INTERMEZZO" For cleaning, the glasses were placed in the dishwasher's upper basket. The dishwashing detergent used was in each case 25 g of formulation according to the invention or 25 g of the comparative formulation according to table 3, table 3 which specifies in each case individually the active components (A.1), mixture of bases, silicate (C.1 or C.2) and compound (D) and / or (E) and (B) of formulation according to the invention . The washing was carried out at a wash-rinse temperature of 55 ° C. The hardness of the water in each case was in the range of 0 to 2o of hardness of Germán. The washing was carried out in each case during a cycle of 100 washes, that is, the program was allowed to run 100 x. The evaluation was made gravimetrically and visually after 100 wash cycles.

The weight of the vessels was determined before starting the first wash cycle and after drying after the last wash cycle. Weight loss is the difference in the two values.

In addition to the gravimetric evaluation, a visual evaluation of the glassware was carried out after 100 cycles in the darkened chamber with light behind a perforated plate using a gradient scale of 1 (very poor) to 5 (very good). In this sense, the degrees in each case were determined for irregular corrosion / opacity and / or corrosion of lines.

Experimental procedure: First, for pretreatment purposes, the test specimens were washed in a household dishwasher (Bosch SGS5602) with 1 g of surfactant (n-Ci8H37 (OCH2CH2) ioOH) and 20 g of citric acid to remove any dirt. The test bodies were dried, their weight determined and fixed to the grid base insert.

To evaluate the gravimetric abrasion, the dry test bodies were weighed. The visual evaluation of the test bodies was carried out then. For this, the surface of the test bodies was evaluated with respect to the corrosion of lines (scraping lines) and turbid corrosion (irregular opacity).

The evaluations were carried out according to the following scheme.

Linear corrosion: L5: no obvious line L4: slight line formation in very few areas, corrosion of fine lines L3: corrosion of lines in some areas L2: corrosion of lines in a number of areas L1: pronounced corrosion of lines Glass turbidity L5: no obvious turbidity L4: slight turbidity in very few areas L3: turbidity in some areas L2: turbidity in a number of areas L1: pronounced turbidity on virtually the entire surface of the glass. In the case of inspection, intermediate degrees were also allowed (for example, L3-4).

If, instead of water, hard water with 2 ° of German hardness was used for the tests, then formulations according to the invention were also always superior to the corresponding comparative formulations always as far as the inhibition of the corrosion of the glass is concerned .

II.3 Results The results are summarized in Table 3.

Only a slight or even no corrosion of the glass was always established in the examples according to the invention

Claims (14)

1. A formulation that is free of heavy metals, comprising (A) in total in the range of 1 to 50% by weight of at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA) and salts thereof, (B) in total in the range from 0.001 to 2% by weight of at least one alkoxylated alkyleneimine polymer with an average molecular weight Mw in the range of 800 to 25,000 g / mol having a positive charge density of at least 5 meq / g and having in the range of 2 a, at most, 80% by weight of alkylene oxide side chains, based on total alkoxylated alkyleneimine polymer, in each case based on the solids content of the formulation in question.

2. The formulation according to claim 1, which is free of phosphates and polyphosphates.

3. The formulation according to claim 1 or 2, wherein (B) is selected from polyethylene imines that were reacted with ethylene oxides or propylene oxides.

4. The formulation according to any of claims 1 to 3, having a heavy metal content of less than 0.05 ppm, based on the solids content of the formulation in question.

5. The formulation according to any of claims 1 to 4, wherein alkyleneimine polymer (B) is selected from those in which at most 30 mole% of the nitrogen atoms of the alkyleneimine polymer were reacted with propylene oxides.

6. The formulation according to any of claims 1 to 5, which is solid at room temperature.

7. The formulation according to any of claims 1 to 6, which comprises in the range of 0.1 to 10% by weight of water.

8. The formulation according to any 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 use of formulations according to any of claims 1 to 8 for washing dishes and kitchen utensils, where the washing is carried out with hard water with 2 to 25 ° hardness of Germán.

10. The use of formulations according to any of claims 1 to 8 for washing objects having at least one surface made of glass, which may be decorated or not decorated.

The use according to claim 9 or 10, wherein the washing is washed using a dishwasher.

12. The use according to any of claims 9 to 11, wherein at least one formulation according to any of claims 1 to 8 is used to wash glasses, glass vases and glass cooking vessels.

13. A process to produce formulations according to any of claims 1 to 8, wherein they are mixed (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 Mw in the range of 800 to 25,000 g / mol having a positive charge density of at least 5 meq / g and having in the range of 2 a, at most, 80% by weight of alkylene oxide side chains, based on total alkoxylated alkyleneimine polymer, and optionally other components in one or more steps with another in the presence of water and then the water is completely or partially removed . The process according to claim 13, wherein the water is removed by spray drying or spray granulation.