EP2768935B1 - Formulations, use thereof as or to produce dishwashing detergents, and production thereof - Google Patents

Description

1. (A) mindestens eine Verbindung, gewählt aus Aminocarboxylaten und Polyaminocarboxylaten,
2. (B) mindestens ein Ethylenimin-Homopolymer,
3. (C) Natriumcitrat und
4. (D) mindestens eine Verbindung, gewählt aus Alkalimetallpercarbonat, Alkalimetallperborat und Alkalimetallpersulfat.

The present invention relates to formulations which are free of phosphates and polyphosphates and which contain

1. (A) at least one compound selected from aminocarboxylates and polyaminocarboxylates,
2. (B) at least one ethyleneimine homopolymer,
3. (C) sodium citrate and
4. (D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.

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

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

Out WO 2010/020765 Dishwashing agents are known which contain polyethyleneimine. Such dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion. Of zinc and bismuth-containing dishwashing detergents is 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.

• (A) mindestens eine Verbindung, gewählt aus Aminocarboxylaten und Polyaminocarboxylaten, im Rahmen der vorliegenden Erfindung kurz auch Aminocarboxylat (A) bzw. Polyaminocarboxylat (A) oder auch Verbindung (A) genannt, sowie deren Derivaten und vorzugsweise Salzen.

Contain formulations according to the invention

• (A) at least one compound selected from aminocarboxylates and polyaminocarboxylates, in the context of the present invention also briefly aminocarboxylate (A) or polyaminocarboxylate (A) or also called compound (A), and their derivatives, and preferably salts.

Compound (A) may be in the form of a free acid or preferably in partially or completely neutralized form, ie as a salt. As counterions, for example inorganic cations, such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg ^2+, preferably Na ^+, K ^+, or organic cations, preferably substituted with one or more organic radicals ammonium, in particular triethanol ammonium, N, N-diethanolammonium , N-mono-C ₁ -C ₄ -alkyldiethanolammonium, for example N-methyl-diethanolammonium or Nn-butyldiethanolammonium, and N, N-di-C ₁ -C ₄ -alkylethanolammonium.

In one embodiment of the present invention, compound (A) is selected from derivatives of aminocarboxylates and polyaminocarboxylates, for example methyl or ethyl esters.

In the context of the present invention, aminocarboxylates (A) are understood as meaning nitrilotriacetic acid and those organic compounds which have a tertiary amino group which has one or two CH ₂ -COOH groups which, as mentioned above, can be partially or completely neutralized or can. In the context of the present invention, polyaminocarboxylates (A) are understood as meaning those organic compounds which have at least two tertiary amino groups which independently of one another have one or two CH ₂ -COOH groups which, as mentioned above, can be partially or completely neutralized or can.

In another embodiment of the present invention, aminocarboxylates (A) are selected from those organic compounds having a secondary amino group having one or two CH (COOH) CH ₂ -COOH group (s) partially as mentioned above or can be completely neutralized. In another embodiment of the present invention, polyaminocarboxylates (A) are selected from those organic compounds having at least two secondary amino groups each containing a CH (COOH) CH ₂ -COOH group which, as mentioned above, partially or completely neutralizes could be.

Preferred polyaminocarboxylates (A) are selected from 1,2-diaminoethanetetraacetic acid, tetraacetylmethylenediamine, tetraacetylhexylenediamine, iminodisuccinate (IDS), diethylenetriamine pentaacetate (DTPA), hydroxyethylenediaminetriacetate (HEDTA), and their respective salts, more preferably alkali metal salts, especially the sodium salts.

Preferred aminocarboxylates (A) and polyaminocarboxylates (A) are nitrilotriacetic acid and those organic compounds having an amino acid-based structure whose amino group (s) have one or two CH ₂ -COOH groups and are tertiary amino groups. It is possible to select amino acids from L-amino acids, R-amino acids and mixtures of enantiomers of amino acids, for example the racemates.

In one embodiment of the present invention, compound (A) is selected from methylglycine diacetate (MGDA), nitrilotriacetic acid and glutamic acid diacetate and their derivatives and preferably their salts, in particular their sodium salts. Very particular preference is given to methylglycine diacetate and to the trisodium salt of MGDA.

Formulation according to the invention furthermore contains (B) at least one homopolymer of ethyleneimine, together referred to in short as polyethyleneimine (B).

According to a particular embodiment of the invention, polyethyleneimine (B) has an average molecular weight M _{n of} from 500 g / mol to 125,000 g / mol, preferably from 750 g / mol to 100,000 g / mol.

In one embodiment of the present invention, polyethyleneimine (B) has an average molecular weight M _w in the range from 500 to 1,000,000 g / mol, preferably in the range from 600 to 75,000 g / mol, particularly preferably in the range from 800 to 25,000 g / mol, determinable for example by gel permeation chromatography (GPC).

mit D (dendritisch) entsprechend dem Anteil tertiärer Aminogruppen, L (linear) entsprechend dem Anteil sekundärer Aminogruppen und T (terminal) entsprechend dem Anteil primärer Aminogruppen.In one embodiment of the present invention, polyethyleneimines (B) are selected from highly branched polyethyleneimines. Highly branched polyethylenimines (B) are characterized by their high degree of branching (DB). The degree of branching can be determined, for example, by ¹³ C-NMR spectroscopy, preferably in D ₂ O, and is defined as follows: $$\mathrm{DB}=\mathrm{D}+\mathrm{T}/\mathrm{D}+\mathrm{T}+\mathrm{L}$$

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

In the context of the present invention, highly branched polyethyleneimines (B) are polyethyleneimines (B) with DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90, particularly preferably in the range from 0.30 to 0.80%. and most preferably at least 0.5.

In the context of the present invention, polyethylene dendrimers (B) which are dendrimeric polyethylenimines (B) are those which have a structurally and molecularly uniform structure.

In one embodiment of the present invention, polyethylenimine (B) is highly branched polyethyleneimines (homopolymers) having an average molecular weight M _w in the range from 600 to 75,000 g / mol, preferably in the range from 800 to 25,000 g / mol.

• (B) um hochverzweigte Polyethylenimine (Homopolymere) mit einem mittleren Molekulargewicht M_n von 500 g/mol bis 125.000 g/mol, bevorzugt von 750 g/mol bis 100.000 g/mol, das aus Dendrimeren gewählt wird.

In a particular embodiment of the invention, polyethyleneimine is used

• (B) highly branched polyethyleneimines (homopolymers) having an average molecular weight M _{n of} from 500 g / mol to 125,000 g / mol, preferably from 750 g / mol to 100,000 g / mol, selected from dendrimers.

Formulations according to the invention also 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.

Formulations according to the invention also 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 formulations according to the invention contain

total in the range of 1 to 50% by weight of compound (A), preferably 10 to 25% by weight, in total 0.05 to 2% by weight of homopolymer of ethyleneimine (B), preferably 0.1 to 0.5 % By weight, 1 to 50% by weight of sodium citrate (C), preferably 5 to 30% by weight, determined as anhydrous sodium citrate,
total 0.5 to 15 wt .-% bleach (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.

Formulation of 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.

In one embodiment of the present invention, the formulation according to the invention is free from those heavy metal compounds which do not function as bleach catalysts, in particular compounds of iron and bismuth. In the context of the present invention, "free from" is to be understood in connection with heavy metal compounds as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in the range from 0 to 100 ppm, determined by the Leach method.

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

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 co-builders, one or more alkali carriers 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 or more tabletting 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

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

R²

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

R³

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

m und n liegen im Bereich von null bis 300, wobei die Summe von n und m mindestens eins beträgt. Bevorzugt ist m im Bereich von 1 bis 100 und n im Bereich von 0 bis 30.Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I)

where the variables are defined as follows:

R ¹

selected from linear C ₁ -C ₁₀ -alkyl, preferably ethyl and more 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-C₄-Alkyl, bevorzugt jeweils gleich und Ethyl und besonders bevorzugt Methyl,

R⁴

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

a

eine Zahl im Bereich von 1 bis 6,

b

ist eine Zahl im Bereich von 4 bis 20,

c

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 ₄ -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,

R ⁴

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

a

a number in the range of 1 to 6,

b

is a number in the range of 4 to 20,

c

is a number in the range of 4 to 25.

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

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

It may also contain mixtures of several different nonionic surfactants.

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

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

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

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

Formulations according to the invention may contain, in addition to sodium citrate, one or more builders, in particular phosphate-free builders. Examples of suitable builders are silicates, especially sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the formula 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 metal malates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example, polycarboxylates and polyaspartic acid.

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

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

It may also be 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 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-hexadecene and 1-octadecene. eicosene, 1-docosene, 1-tetracosene, and 1-hexacosene, C ₂₂ -α-olefin, a mixture of C ₂₀ -C ₂₄ -α-olefins and polyisobutene having on average 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 in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.

Formulations of the invention may contain one or more alkali carriers. Alkaline carriers, for example, provide the pH of at least 9 when an alkaline pH is desired. Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates. Preferred alkali metal is in each case potassium, particularly preferred is sodium.

Formulations according to the invention, in addition to bleach (D), contain one or more chlorine-containing bleaches.

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

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

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-hexahydro-1 , 3,5-triazine ("DADHT") or nitrile quats (trimethylammonium acetonitrile salts).

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.

Preferred is the use of formulations according to the invention for machine cleaning of articles which have at least one surface of glass which may be decorated or not decorated. In the context of the present invention, a surface of glass is to be understood as meaning that the object in question has at least one piece of glass which comes into contact with the ambient air and 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.

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.

A further subject of the present invention is a process for the preparation of formulations according to the invention as defined in claim 12. 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 removed completely or partially, for example to a residual moisture in the range from zero to 5% by weight, from the formulation according to the invention by evaporation, in particular by spray drying, spray granulation or compaction.

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

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

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

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

The invention is illustrated by working examples.

• I. Herstellung erfindungsgemäßen Formulierungen
• I.1 Herstellung von Basismischungen

Zunächst wurden Basismischungen hergestellt, die die Einsatzstoffe gemäß Tabelle 1 enthielten. Die Einsatzstoffe wurden trocken vermischt. Tabelle 1: Basismischungen für Versuche mit erfindungsgemäßen Formulierungen und Vergleichsformulierungen Basis-1 Basis-2 Basis-3 Protease 2,5 2,5 2,5 Amylase 1 1 1 n-C₁₈H₃₇(OCH₂CH₂)₉OH 5 5 5 Polyacrylsäure M_w 4.000 g/mol als Natriumsalz, vollständig neutralisiert 10 10 10 Natriumpercarbonat (D.1) 10,5 10,5 10,5 TAED 4 4 4 Na₂Si₂O₅ 2 2 2 Na₂CO₃ 19,5 19,5 19,5 Natriumcitrat Dihydrat (C.1) 5 22,5 30 HEDP 0,5 0,5 0,5 Alle Mengeangaben in gGeneral: Care was taken that after the first cleaning of the specimens in the household dishwasher until after weighing and visual patterning of the glasses, the specimens were only touched with clean cotton gloves, so that the weight or the visual impression of the specimens was not falsified.

• I. Preparation of formulations according to the invention
• I.1 Preparation of basic mixtures

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

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

Abbreviations:

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

I.2 Preparation of formulations according to the invention

• Polyethylenimin (B.1), (B.2), (B.3), (B.4) oder (B.5) gemäß Tabelle 2 (oder 3)

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

• Polyethyleneimine (B.1), (B.2), (B.3), (B.4) or (B.5) according to Table 2 (or 3)

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

There were obtained formulations according to the invention, which were tested according to Table 2 (or 3). The comparative formulations were prepared analogously, but omitting the polyethyleneimine (B) or using a copolymer of ethyleneimine.

• (B.1): Polyethylenimin-Homopolymer, M_w 800 g/mol, DB 0,63
• (B.2): Polyethylenimin-Homopolymer, M_w 2.000 g/mol, DB 0,64
• (B.3): Polyethylenimin-Homopolymer, M_w 5.000 g/mol, DB 0,67
• (B.4): Polyethylenimin-Homopolymer, M_w 25.000 g/mol, DB 0,7
• (B.5) Polyethylenimin-Homopolymer, M_w 750.000 g/mol, DB 0,69
• (B.6) Polyethylenimin, ethoxyliert
• (B.7) Polyethylenimin, carboxymethyliert, Natriumsalz, Funktionalisierung 80 mol-% der primären Aminogruppen, M_w 50.000 g/mol (nach Carbomethoxylierung)

If one dosed the corresponding proportions of the base mixture separately from the aqueous solution of (A.1), (B), (C.1) or (D.1) in the test dishwasher with endurance runner (or immersion test), the same results were obtained. as if testing the dried formulation with equal amounts of active ingredients. So it does not depend on the order of the dosage.

• (B.1): Polyethyleneimine homopolymer, M _w 800 g / mol, DB 0.63
• (B.2): Polyethyleneimine homopolymer, M _w 2,000 g / mol, DB 0.64
• (B.3): Polyethyleneimine homopolymer, M _w 5,000 g / mol, DB 0.67
• (B.4): Polyethyleneimine homopolymer, M _w 25,000 g / mol, DB 0.7
• (B.5) Polyethyleneimine homopolymer, M _w 750,000 g / mol, DB 0.69
• (B.6) Polyethyleneimine, ethoxylated
• (B.7) polyethyleneimine, carboxymethylated, sodium salt, functionalization 80 mol% of the primary amino groups, M _w 50,000 g / mol (after carbomethoxylation)

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

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

II.1 Test method Dishwasher with endurance runner

Dishwasher:

Miele G 1222 SCL

Program:

65 ° C (with pre-rinse)

ware:

3 champagne glasses "GILDE", 3 shot glasses, "INTERMEZZO"

For cleaning, the glasses were placed in the upper basket of the dishwasher. The dishwashing agent used was in each case 25 g of formulation according to the invention or comparison formulation according to Table 2, where Table 2 shows the active components (A.1), base mixture (including (C.1) and (D.1) and optionally (B) each formulation according to the invention was rinsed separately at a rinse temperature of 55 ° C. The water hardness was in each case in the range from zero to 2 ° dH 100 wash cycles in each case, ie, the program was run 100 times, and the evaluation was carried out gravimetrically and visually after 100 wash cycles.

The weight of the glasses was determined before the beginning of the first rinse cycle and after drying after the last rinse cycle. The weight loss is the difference between the two values.

In addition to the gravimetric evaluation, a visual evaluation of the washware was given after 100 cycles in a darkened chamber under light behind a pinhole using a grading scale from 1 (very poor) to 5 (very good). In each case grades for area corrosion / turbidity or line corrosion were determined.

II.2 Test method Immersion test Equipment:

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

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

Test conditions:

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

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

• Zunächst spülte man zum Zwecke der Vorbehandlung die Prüfkörper in einer Haushaltsgeschirrspülmaschine (Bosch SGS5602) mit einem 1 g Tensid (n-C₁₈H₃₇(OCH₂CH₂)₁₀OH) und 20 g Zitronensäure, um eventuelle Verunreinigungen zu entfernen. Man trocknete die Prüfkörper, bestimmte ihr Gewicht und fixierte sie auf dem Gitterbodeneinsatz.

Experimental procedure:

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

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

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

To assess the gravimetric removal, the dry specimens were weighed. This was followed by the visual assessment of the test specimens. 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.

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

Line corrosion:

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

• T5: keine Trübung zu erkennen
• T4: in sehr wenigen Bereichen geringe Trübung
• T3: in einigen Bereichen Trübungen
• T2: in mehreren Bereichen Trübungen
• T1: Stark ausgeprägte Trübung über fast die ganze Glasoberfläche

glass opacity

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

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

If hardness water at 2 ° dH was used instead of water for the tests, formulations according to the invention were also always superior to the corresponding comparative formulations in terms of the inhibition of glass corrosion. Table 2: 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 3: 21.25 3.75 - 42,60 22.70 L1-2, T1-2 L2, T2 2 Base 3: 21.25 3.75 30 (B.2) 11 7 L3-4, T4-5 L4, T4-5 3 Base 3: 21.25 3.75 15 (B.2) 13 8th L3, T4-5 L3-4, T4-5 4 Base 2: 19.37 5.63 30 (B.2) 14 8th L3, T4-5 L3-4, T4-5 5 Base 2: 19.37 5.63 15 (B.2) 17 10 L3, T4-5 L2-3, T4-5 6 Base 1: 15.0 10.0 30 (B.2) 21 12 L2-3, T4-5 L2-3, T4 7 Base 1: 15.0 10.0 15 (B.2) 23 14 L2-3, T4 L2-3, T4 8th Base 3: 21.25 3.75 30 (B.1) 9 6 L4, T5 L4, T5 9 Base 3: 21.25 3.75 15 (B.1) 12 9 L3-4, T5 L4, T4-5 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 3: 21.25 3.75 --- 167 98 L2, T2 L2, T2 2 Base 3: 21.25 3.75 30 (B.5) 148 92 L2-3, T2-3 L2, T2-3 3 Base 3: 21.25 3.75 30 (B.4) 100 55 L3, T4-5 L3, T4-5 4 Base 3: 21.25 3.75 30 (B.3) 70 38 L3, T4-5 L3-4, T4-5 5 Base 3: 21.25 3.75 30 (B.2) 62 33 L3-4, T5 L4, T4-5 6 Base 3: 21.25 3.75 30 (B.1) 58 31 L3-4, T5 L4, T5 V-7 Base 3: 21.25 3.75 30 (B.6) 152 89 L2-3, T2-3 L2, T2-3 V-8 Base 3: 21.25 3.75 30 (B.7) 122 75 L2-3, T3-4 L2, T3-4 9 Base 3: 21.25 3.75 7.5 (B.1) 73 40 L2-3, T4-5 L2, T4-5 10 Base 3: 21.25 3.75 12 (B.1) 68 39 L2-3, T4-5 L2-3, T4-5 11 Base 3: 21.25 3.75 16.5 (B.1) 63 35 L3, T4-5 L3, T4-5 12 Base 3: 21.25 3.75 24 (B.1) 60 33 L3-4, T5 L4, T4-5

Claims (13)

1. A formulation which is free from phosphates and polyphosphates, comprising

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

   (B) at least one ethyleneimine homopolymer,

   (C) sodium citrate and

   (D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.
2. The formulation according to claim 1, wherein (B) is selected from linear and branched homopolymers of ethyleneimine.
3. The formulation according to claim 1 or 2, which has a heavy metal content below 0.05 ppm, based on the solids content of the formulation in question.
4. The formulation according to any one of claims 1 to 3, wherein compound (A) is selected from methylglycine diacetate (MGDA), nitrilotriacetic acid and glutamic acid diacetate, and salts and derivatives thereof.
5. The formulation according to any one of claims 1 to 4, which is solid at room temperature.
6. The formulation according to any one of claims 1 to 5, which comprises in the range from 0.1 to 10% by weight of water.
7. The formulation according to any one of claims 1 to 6, which comprises:

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

   in total in the range from 0.05 to 2% by weight of ethyleneimine homopolymer (B),

   in the range from 1 to 50% by weight of sodium citrate (C) and

   in total in the range from 0.5 to 15% by weight of compound (D),

   based in each case on the solids content of the formulation in question.
8. The use of formulations according to any one of claims 1 to 7 for washing dishes and kitchen utensils.
9. The use of formulations according to any one of claims 1 to 7 for washing objects which have at least one surface made of glass, which may be decorated or undecorated.
10. The use according to claim 8 or 9, wherein the washing is washing using a dishwasher.
11. The use according to any one of claims 8 to 10, wherein at least one formulation according to any one of claims 1 to 7 for washing drinking glasses, glass vases and glass vessels for cooking is used.
12. A process for producing formulations according to any one of claims 1 to 7, wherein

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

    (B) at least one ethyleneimine homopolymer,

    (C) sodium citrate and

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

    and optionally further components are mixed in one or more steps with one another in the presence of water and then the water is removed.
13. The process according to claim 12, wherein the water is removed by spray-drying.