EP2961822A1

EP2961822A1 - Formulations, use thereof as dishwashing detergents or for producing dishwashing detergents, and the production of said formulations

Info

Publication number: EP2961822A1
Application number: EP14702846.8A
Authority: EP
Inventors: Stephan Hüffer; Sophia Ebert; Björn LUDOLPH; Christoph Müller; Alejandra Garcia Marcos
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2013-02-28
Filing date: 2014-02-04
Publication date: 2016-01-06
Anticipated expiration: 2034-02-04
Also published as: US10301576B2; WO2014131585A1; EP2961822B1; US20150361379A1; ES2632465T3; PL2961822T3

Abstract

The invention relates to a formulation containing (A) at least one amino carboxylate, selected from methylglycinediacetate (MGDA), iminodisuccinic acid (IDS), glutamic acid diacetate (GLDA), and the salts thereof, and (B) at least one polypropylene imine which can be alkoxylated.

Description

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

The present invention relates to formulations containing

(A) at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and (B) at least one polypropyleneimine which may be alkoxylated.

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 thoroughly clean the dishes, they should have no harmful or potentially harmful substances in the wastewater, they should allow the draining and drying of the water from the dishes, and they should not cause problems when operating the dishwasher. Finally, they should not lead to aesthetically undesirable consequences on the good to be cleaned. Especially in this context is the glass corrosion. Glass corrosion is caused not only by mechanical effects, for example, by juxtaposition of glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences. For example, certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.

Glass corrosion has several effects. On the one hand, one can observe the formation of microscopically fine cracks, which are noticeable in the form of lines. On the other hand, one can often observe a general cloudiness, for example a roughening, which makes the glass in question look unaesthetic. Overall, such effects are also subdivided into iridescent discoloration, scoring and surface and annular opacities.

WO 2006/108857 discloses alkoxylated polyethyleneimines as additives to detergents. Detergents containing zeolites or polyaminocarboxylates such as EDTA or triethylenediamine pentaacetate as complexing agents are disclosed by way of example.

WO 01/96516 proposes formulations containing alkoxylated polyethylenimine for cleaning hard surfaces. For rinsing, purified water is used. From WO 2010/020765 dishwashing agents are known which contain polyethyleneimine. Such dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion. Of zinc and bismuth-containing dishes Dishwashing 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. There was also the task of making use of formulations ready to provide.

Accordingly, the formulations defined above were found, also called formulations according to the invention. Contain formulations according to the invention

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

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

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

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

Formulations according to the invention also contain

(B) at least one polypropyleneimine which may be alkoxylated.

Alkoxylated polypropyleneimines are also referred to in the context of the present invention as "modified polypropyleneimine (B)" or "alkoxylated polypropyleneimine (B)". Non-alkoxylated polypropyleneimine is also referred to in the context of the present invention as "polypropyleneimine (B)" for short. In one embodiment of the present invention, polypropyleneimine (B) has a molecular weight M _n in the range of 300 to 4,000 g / mol, preferably 400 to 2,000 g / mol.

In one embodiment of the present invention, modified polypropyleneimine (B) has an average molecular weight M _w in the range of 800 to 25,000 g / mol.

The term polypropyleneimine in the context of the present invention does not only refer to homopolymers of propylenediamine, but also to those polyalkyleneimines which, in addition to NH-CH ₂ -CH ₂ -CH ₂ -NH units and / or NH-CH ₂ -CH (CH ₃ ) -NH units have other alkylenediamine units, for example NH-CH ₂ -CH ₂ -NH units, NH- (CH ₂ ) 4 -NH units, NH- (CH ₂ ) ₆ -NH units or NH- (CH ₂ ) ₈ -NH units, but where molar are NH-CH ₂ -CH ₂ -CH ₂ -NH units and / or NH-CH ₂ -CH (CH 3) -NH units in the majority , Preferred polypyrimines have, for example, at least 60 mol% of propylene imine units per molecule, more preferably at least 70 mol%.

In a particularly preferred embodiment, the term polypropyleneimine refers to those polyalkyleneimines which have only one or no structural element other than NH-CH ₂ -CH ₂ -CH ₂ -NH. Polypropyleneimine can be linear, predominantly linear or branched, predominantly linear is preferred, and linear is particularly preferred. The structure of polypropyleneimine can be controlled by the nature of the synthesis. Polypropyleneimine in the context of the present invention may also be referred to as polypropylene polyamines. Polypropyleneimines in the context of the present invention have at least 6 N atoms per molecule, for example as NH ₂ groups, as secondary amino groups or as tertiary amino groups.

Branches of polypropyleneimines may be, for example, CH ₂ -CH ₂ -NH ₂ groups, or (CH ₂ ) 3 -NH ₂ units. For example, larger branches can be used

- (CH ₂ ) 3-N (CH ₂ CH ₂ CH ₂ NH ₂ ) ₂ units. Highly branched polypropyleneimines can be, for example, polypropylene end-dendrimers or related molecules, for example with a degree of branching (DB) in the range from 0.25 to 0.95, preferably from 0.3 to 0.80 and particularly preferably from at least 0.5. The degree of branching of polypropyleneimines can also be determined by ¹³ C-NMR or ¹⁵ N-NMR spectroscopy, preferably in D ₂ O, and is defined as follows:

DB = D + T / D + T + L with D (dendritic) corresponding to the proportion of tertiary amino groups, L (linear) corresponding to the proportion of secondary amino groups and T (terminal) corresponding to the proportion of primary amino groups. Methyl groups are not considered as branches in the context of the present invention.

However, preference is given to polypropyleneimines having little or no branching, that is to say predominantly linear and in particular linear polypropyleneimines. In some embodiments of the present invention, polypropyleneimine can be prepared by catalytic polycondensation of propanolamine and optionally at least one further aminoalcohol or by catalytic polycondensation of propanediol with propandiamine and optionally at least one further diol and / or at least one further diamine. Polypropyleneimine is preferably prepared by catalytic polycondensation of propanediamine with optionally at least one further diamine. The latter type of polycondensation is also referred to as transamination. Other amino alcohols, diols and diamines are selected from aliphatic aminoalcohols, aliphatic diols and aliphatic diamines. Examples of aminopropanols are 3-amino-1-propanol, 1-amino-2-propanol and 2-amino-1-propanol and mixtures of the abovementioned aminopropanols, with 3-amino-1-propanol being preferred. Optionally, in the preparation of polypropyleneimines obtainable by polycondensation of aminoalcohols, up to 40 mole% of aminopropanol, preferably up to 30 mole% of aminopropanol may be replaced by one or more amino alcohols bearing one hydroxy group and one primary or secondary amino group per mole.

Examples of further amino alcohols are linear or branched amino alcohols, for example monoethanolamine, diethanolamine, aminobutanol, for example 4-aminobutan-1-ol, 2-aminobutan-1-ol or 3-aminobutan-1-ol, aminopentanol, for example 5-aminopentane -1 -ol or 1-aminopentan-2-ol, aminodimethylpentanol, for example 5-amino-2,2-dimethylpentanol, aminohexanol, for example 2-aminohexan-1-ol or 6-aminohexan-1-ol, aminoheptanol, for Example 2-aminoheptan-1-ol or 7-aminoheptan-1-ol, amino octanol, for example 2-aminooctan-1-ol or 8-aminooctan-1-ol, aminononanol, for example 2-aminononan-1-ol or 9 Aminonan-1-ol, aminodecanol, for example 2-aminodecan-1-ol or 10-aminodecan-1-ol, aminoundecanol, for example 2-aminoundekane-1-ol or 1-amino-edekan-1-ol, aminodecanol kanol, for example 2-aminododecan-1-ol or 12-aminododecan-1-ol, aminotridecanol, for example 2-aminotridecan-1-ol, wherein the respective ω-amino-a-alcohols relative to their 1, 2- I each of which is preferred, 2- (2-aminoethoxy) ethanol, alkylalkanolamines, for example N-n-butylethanolamine, Nn-propylethanolamine, N-ethylethanolamine and N-methylethanolamine. Preference is given to monoethanolamine. In one embodiment of the present invention, polypropyleneimine is obtained by catalytic polycondensation of 3-aminopropan-1-ol without the addition of aminoalcohol other than 3-aminopropan-1-ol. Examples of propanediamines and propanediols which can be processed by poly-co-condensation to polypropyleneimine are described below. The terms "propylenediamine" and "propanediamine" are used synonymously in the context of the present invention. Examples of propanediamines are propane-1,2-diamine and propane-1,3-diamine and mixtures of the above, with propane-1,3-diamine being preferred. Examples of the corresponding propanediols are propane-1,3-diol and propane-1,2-diol and mixtures of the above, with propane-1,3-diol being preferred. In the case of poly-co-condensation, the poly-co-condensation of propane-1, 3-diol with propane-1, 3-diamine is preferred.

Optionally, one can replace up to 40 mol% of the sum of propanediamine and propanediol by one or more aliphatic diols or aliphatic diamines, each of which is different from propanediol or propanediamine, in particular up to 30 mol%.

Examples of other aliphatic diols are linear or branched diols. Specific examples are ethylene glycol, 2-methyl-1,3-propanediol, butanediols, for example 1,4-butylene glycol or butane-2,3-diol or 1,2-butylene glycol, pentanediols, for example neopentyl glycol or 1,5-pentanediol or 1, 2-pentanediol, hexanediols, for example 1, 6-hexanediol or 1, 2-hexanediol, heptanediols, for example 1, 7-heptanediol or 1, 2-heptanediol, octanediols, for example 1, 8-octanediol or 1 , 2-octanediol, nonanediols, for example 1, 9-nonanediol or 1, 2-nonanediol, decandiols, for example 1, 10-decanediol or 1, 2-decanediol, undecanediols, for example 1, 1 1 - undecanediol or 1,2-undecanediol, dodecanediols, for example 1,12-dodecanediol or 1,2-dodecanediol, tridekanediols, for example 1,13-tridecanediol or 1,2-tridecanediol, tetradecanediols, for example 1,1,4-tetradecanediol or 1, 2-tetradecanediol, pentadecanediols, for example 1, 15-pentadecanediol or 1, 2-pentadecanediol, hexadecanediols, for example 1, 16-hexadecanediol or 1, 2-hexadecanediol, He ptadekandiole, for example 1, 17-heptadekandiol or 1, 2-heptadekandiol, octadecanediols, for example 1, 18-octadecanediol or 1, 2-

Octadecanediol, wherein the respective α, ω-diols are preferred over their 1, 2-isomers, 3,4-dimethyl-2,5-hexanediol, Ν, Ν-diethanolamines, for example Nn-butyldiethanolamine or N-methyldiethanolamine, and others dialcoholamines. Preference is given to ethylene glycol. Examples of other aliphatic diamines are linear or branched diamines. Specific examples are ethylenediamine, butylenediamines, for example 1,4-butylenediamine or 1,2-butylenediamine, diaminopentanes, for example 1,5-diaminopentane or 1,2-diaminopentane, diaminohexane, for example 1,6-diaminohexane, 1,5 Diamino-2-methylpentane or 1,2-diaminohexane, diaminoheptane, for example 1,7-diaminoheptane or 1,2-diaminoheptane, diaminooctane, for example 1,8-diaminooctane or 1,2-diaminooctane, diaminononane, for example Example 1, 9-diaminononane or 1, 2-diaminononane, diaminodecane, for example 1, 10-diaminodecane or 1, 2-diaminodecane, diaminoundekane, for example 1, 1 1 -Diaminoundekan or 1,2-diaminoundekane, diaminododecane, for example 1,12-diaminododecane or 1,2-diaminododecane, the respective α, ω-diamines being preferred over their 1,2-isomers, 2,2-dimethylpropane-1,3 -diamine, 4,7,10-trioxatridekan-1, 13-diamine, 4,9-dioxadodecane-1, 12-diamine, and 3- (methylamino) propylamine. Preference is given to 1, 2-ethylenediamine and 1, 4-butanediamine.

In the context of the present invention, compounds having two NH ₂ groups and one tertiary amino group, for example N, N-bis (3-aminopropyl) methylamine, are also to be considered as diamines.

In a preferred embodiment of the present invention, polypropyleneimine is prepared by catalytic poly-co-condensation of 1,3-propylene glycol with 1,3-propanediamine, without the use of diols and diamines derived from 1,3-propylene glycol and 1, respectively. 3- Propandiamine are different.

The above-described polycondensations or poly-co-condensations can be carried out in the absence or in the presence of hydrogen, for example under a hydrogen pressure in the range from 1 to 10 MPa. The polycondensations or poly-co-condensations described above can be carried out at a temperature in the range from 20 to 250.degree. C., preferably at least 100 and at most 200.degree.

During the polycondensations or poly-co-condensations described above, the water formed during the reaction can be removed, for example by distillation.

Suitable catalysts for the above-described polycondensations or poly-co-condensations can preferably be selected from homogeneous catalysts. Suitable homogeneous catalysts can be used in activated form or activated in situ during the polycondensation or poly-co-condensation.

Examples of catalysts for homogeneous catalysis are Ru (p-cumene) Cl 2] 2, [Ru (benzene) Cl 2] _y , [Ru (CO) ₂ Cl ₂ ] y, where y is in the range from 1 to 1000, [Ru (CO) ₃ Cl ₂ ] 2, [Ru (COD) (allyl)], RuCl ₃ -H ₂ O, [Ru (acetylacetonate) ₃ ], [Ru (DMSO) ₄ Cl ₂ ], [Ru (Cp) ( CO) ₂ Cl], [Ru (Cp) (CO) ₂ H],

[Ru (Cp) (CO) ₂ ] ₂ , [Ru (Cp) (CO) ₂ Cl], [Ru (Cp ^* ) (CO) ₂ H], [Ru (Cp ^* ) (CO) ₂ ] ₂ , [Ru (indenyl) (CO) ₂ Cl], [Ru (indenyl) (CO) ₂ H], [Ru (indenyl) (CO) ₂ ] ₂ , ruthenocene, [Ru (COD) Cl ₂ ] ₂ , [Ru (Cp ^* ) (COD) CI],

[Ru ₃ (CO) i ₂ ], [Ru (PPh ₃ ) ₄ (H) ₂ ], [Ru (PPh ₃ ) ₃ (CI) ₂ ], [Ru (PPh ₃ ) ₃ (CO) (CI) ₂ ], [Ru (PPh ₃₎ ₃ (CO) (CI) (H)], [Ru (PPh ₃₎ ₃ (CO) (H) _2] and [Ru (Cp) (methylallyl) _2], [Ru ( bipy) ₂ Cl ₂ -2H20], [Ru (COD) Cl _2] _2,

[Ru (Cp ^* ) (COD) Cl], [Ru ₃ (CO) i ₂ ], [Ru (tetraphenylhydroxy-cyclopentadienyl) (CO) ₂ H],

[Ru (PMe ₃₎ ₄ (H) _2], [Ru (PEt ₃₎ ₄ (H) _2], [Ru (P (n-Pr) ₃₎ ₄ (H) _2], [Ru (P (n -Bu) ₃ ) ₄ (H) ₂ ], [Ru (Pn-Octyl ₃ ) ₄ (H) ₂ ], [IrCl ₃ -H ₂ O], KlrCU, K ₃ IrCI ₆ , [Ir (COD) Cl] ₂ , [Ir (cyclooctene) ₂ Cl] ₂ , [Ir (ethene) ₂ Cl] ₂ , [Ir (Cp) Cl ₂ ] ₂ , [Ir (Cp ^* ) Cl ₂ ] 2, [Ir (Cp) (CO) ₂ ], [Ir (Cp ^* ) (CO) 2], [Ir (PPh ₃ ) 2 (CO) (H)], [ Ir (PPh ₃ ) 2 (CO) (Cl)], [Ir (PPh ₃ ) ₃ (Cl)] where the synthesis of the catalysts can be carried out by reaction of commercially available compounds and the corresponding ligands. In the context of the present invention, the variables have the following meaning, Cp means cyclopentadienyl and Cp ^* means pentamethylcyclopentadienyl. COD is cycloocta-1, 5-dienyl, Et: ethyl, Me: methyl, Ph: phenyl, n-Pr: n-propyl, n-Bu: n-butyl, bipy: 2,2'-bipyridyl. In one embodiment of the present invention, polypropyleneimines prepared by the polycondensation or poly-co-condensation described above have an OH number in the range of 1 to 1000 mg KOH / g, preferably 2 to 500 mg KOH / g, more preferably from 10 to 300 mg KOH / g. The OH number can be determined according to DIN 53240. In one embodiment of the present invention, polypropyleneimines prepared by the above-described polycondensation or poly-co-condensation have a primary amine value in the range of 1 to 1,000 mg KOH / g, preferably 10 to 500 mg KOH / g preferably 50 to 300 mg KOH / g. One can determine the primary amine number according to ASTM D2074-07.

In one embodiment of the present invention, polypropyleneimines prepared by the polycondensation or poly-co-condensation described above have a secondary amine value in the range of 1 to 1000 mg KOH / g, preferably 10 to 500 mg KOH / g, more preferably 50 up to 300 mg KOH / g. The secondary amine number can be determined according to ASTM D2074-07.

In one embodiment of the present invention, polypropyleneimines prepared by the polycondensation or poly-co-condensation described above have a tertiary amine value in the range of 1 to 300 mg KOH / g, preferably 5 to 200 mg KOH / g, more preferably 10 to 100 mg KOH / g. The tertiary amine number can be determined according to ASTM D2074-07.

In one embodiment of the present invention, the molar proportion of tertiary amine nitrogens is determined by ¹⁵ N NMR spectroscopy. In cases where the tertiary amine number and the values for the tertiary amine nitrogen atoms were inconsistent by ¹⁵ N-NMR spectroscopy, the values determined by means of ¹⁵ N-NMR spectroscopy apply.

In a preferred embodiment of the present invention, polypropyleneimines can be obtained by catalytic transamination of propanediamine and optionally at least one further diamine. Examples of propanediamines are 1, 2-propanediamine and 1, 3-propanediamine. Particularly preferred are transaminations of 1, 3-propanediamine. Optionally, up to 40 mol% of propanediamine can be replaced by one or more propanediamine-different aliphatic diamines, in particular up to 30 mol%. Examples of other aliphatic diamines are linear or branched diamines. Specific examples are ethylenediamine, butylenediamines, for example 1,4-butylenediamine or 1,2-butylenediamine, diaminopentanes, for example 1,5-diaminopentane or 1,2-diaminopentane, diaminohexane, for example 1,6-diaminohexane, 1,5 Diamino-2-methylpentane or 1,2-diaminohexane, diaminoheptane, for example 1,7-diaminoheptane or 1,2-diaminoheptane, diaminooctane, for example 1,8-diaminooctane or 1,2-diaminooctane, diaminononane, for example Example 1, 9-diaminononane or 1, 2-diaminononane, diaminodecane, for example 1, 10-diaminodecane or 1, 2-diaminodecane, diaminoundekane, for example 1, 1 1 -diaminoundekane or 1, 2-diaminoundekane, diaminododecane, for example 1,2-diaminododecane or 1,2-diaminododecane, the particular α, ω-diamines being preferred over their 1,2-isomers, 2,2-dimethylpropane-1,3-diamine, 4,7,10-trioxatridane 1, 13-diamine, 4,9-dioxadodecane-1, 12-diamine and 3- (methylamino) propylamine. Preference is given to 1, 2-ethylenediamine and 1, 4-butanediamine.

In the context of the present invention, compounds having two Nh groups and one tertiary amino group, for example N, N-bis (3-aminopropyl) methylamine, are also to be regarded as diamines.

In a particularly preferred embodiment of the present invention is obtained polyp ropylenimin by catalytic transamination of 1, 3-propanediamine, without the addition of a different of 1, 3-propanediamine diamine.

Catalysts suitable for the transamination of propanediamine and optionally at least one further diamine are preferably heterogeneous catalysts containing at least one transition metal selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt, preferably of Co, Ni, Ru, Cu and Pd, and more preferably of Co, Ni and Cu. The abovementioned metals may also be referred to as "catalytically active metals" in the context of the present invention.

In one embodiment of the present invention, a catalytically active metal may be doped with one or more promoters other than the catalytically active metal, for example with Cr, Co, Mn, Mo, Ti, Sn, alkali metal, alkaline earth metal or phosphorus.

Preference is given to using a Raney type catalyst, which can be obtained by activating an alloy of a catalytically active metal with another metal, preferably aluminum. Preferred are Raney nickel and Raney cobalt. In one embodiment of the present invention, a supported Pd catalyst or a supported Pt catalyst may be employed. Examples of suitable support materials are carbon, for example as activated carbon, further AI2O3, ΤΊΟ2, ZrÜ2 and S1O2. Particular preference is given to catalysts which can be obtained by reducing a catalyst precursor.

Catalyst precursors contain an active mass of precursors of one or more catalytically active components, optionally one or more promoters and optionally a carrier material.

The catalytically active components are oxygen-containing compounds of the abovementioned catalytically active metals, for example their metal oxides or hydroxides, such as CoO, NiO, CuO and / or their mixed oxides.

The transamination of propanediamine and optionally further diamine can be carried out in the absence or in the presence of hydrogen, for example under a hydrogen pressure in the range from 1 to 400 bar, preferably up to 200 bar and particularly preferably up to 100 bar.

The transamination of propanediamine and optionally further diamine can be carried out at a temperature in the range of 50 to 200 ° C, preferably 90 to 180 ° C and particularly preferably 120 to 160 ° C. The transamination of propanediamine and optionally further diamine can be carried out at a pressure in the range from 1 to 400 bar, preferably up to 200 bar and particularly preferably up to 100 bar.

The transaminations of propanediamine described above give linear polypropyleneimine.

A polypropyleneimine which has no hydroxyl groups is obtained. The OH number according to DIN 53240 is accordingly zero. This statement naturally refers to the polypropyleneimine prior to the alkoxylation.

In one embodiment of the present invention, polypropyleneimines prepared by the transamination described above have a primary amine value in the range of 10 to 1000 mg KOH / g, preferably 80 to 800 mg KOH / g, more preferably 100 to 500 mg KOH / g , One can determine the primary amine number according to ASTM D2074-07.

In one embodiment of the present invention, polypropyleneimines prepared by the transamination described above have a secondary amine number in the range from 100 to 2,000 mg KOH / g, preferably from 200 to 1,500 mg KOH / g, more preferably from 300 to 1, 000 mg KOH / g. The secondary amine number can be determined according to ASTM D2074-07.

In one embodiment of the present invention, polypropyleneimines prepared by the transamination described above have zero to 2 mole percent tertiary amine.

Nitrogen atoms, based on all N atoms in the molecule in question. The molar fraction of the tertiary amine nitrogen atoms is preferably determined by ¹⁵ N-NMR spectroscopy.

In a preferred embodiment of the present invention, the average molecular weight M _n of polypropyleneimine (B) is in the range from 300 to 4,000 g / mol, particularly preferably in the range from 400 to 2,000 g / mol. The average molecular weight M _n can be obtained, for example, by gel permeation chromatography (GPC) or by end group analysis, for example by NMR spectroscopy. In a preferred embodiment of the present invention, the width of the molecular weight distribution Mw Mn of polypropyleneimine (B) is in the range of 1.2 to 20, preferably in the range of 1.5 to 7.5.

In one embodiment of the present invention, the cationic charge density of alkoxylated polypropyleneimine is in the range of 4 to 22 meq / g dry matter, preferably in the

Range of 6 to 18 meq / g dry matter, determined at a pH in the range of 3 to 4 by titration.

Polypropyleneimine (B) is used in one embodiment of the present invention in a covalently modified form in such a way that preferably 90 to 100 mol% of the nitrogen atoms of the primary and secondary amino groups of the polypropyleneimine (B) are alkoxylated. For the alkoxylation one can use epoxides, for example ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide or epichlorohydrin. Preferred alkoxylation reagents are butylene oxide, ethylene oxide and propylene oxide as well as combinations of ethylene oxide and propylene oxide. If one uses combinations of ethylene oxide and propylene oxide, it is possible to incorporate the various alkylene oxides blockwise or statistically.

In one embodiment of the present invention, modified polypropyleneimine (B) is selected from polypropyleneimines that are alkoxylated with ethylene oxide or propylene oxide. In particular, alkoxylated modified polypropyleneimine (B) is used with ethylene oxide as the sole alkylene oxide.

In one embodiment of the present invention, the molar ratio of nitrogen atoms to alkylene oxide groups in modified polypropyleneimine (B) is in the range of 1: 1 to 1: 00, preferably in the range of 1: 2 to 1:15. The alkoxylation of polypropyleneimine (B) can be carried out, for example, as follows, and the alkoxylation is preferably carried out as a catalytic alkoxylation. Examples of suitable catalysts are Lewis acids, for example AlC or BF 3 etherate, BF 3, BF 3 Ή3ΡΟ4, SbCl 2 -2H 2 O and hydrotalcite. Preferred catalysts are strong bases, for example potassium hydroxide, sodium hydroxide, potassium or sodium alcoholates such as, for example, potassium methylate (KOCH3), sodium methoxide (NaOCHs), potassium ethanolate, sodium ethanolate and potassium tert-butoxide. Other suitable strong bases are sodium hydride, calcium hydride and alkali metal carbonates such as sodium carbonate and potassium carbonate. Particularly preferred catalysts are alkali metal hydroxides and alkali metal alcoholates, most preferably sodium hydroxide and potassium hydroxide. In general, it is possible to use 0.05 to 10% by weight of catalyst, preferably 0.5 to 2% by weight, based on the sum of polypropyleneimine and alkylene oxide.

In one embodiment of the present invention, the alkoxylation is carried out at a temperature in the range of 90 to 240 ° C, preferably in the range of 120 to 180 ° C, in a closed vessel, for example in an autoclave.

In one embodiment of the present invention, the alkoxylation is carried out at a pressure in the range from 1 to 10 bar, preferably up to 8 bar.

In one embodiment of the present invention, alkylene oxide (e) and polypropyleneimine and, if appropriate, catalyst are reacted with one another under the vapor pressure of the relevant alkylene oxide or of the mixture of the respective alkylene oxides at the selected temperature.

Alkylene oxide (s) can be introduced in pure form or, as an alternative, in a form diluted with inert gas, for example in 30 to 60% by volume mixture. Examples of suitable inert gases are noble gases and in particular nitrogen. A dilution can be chosen, for example, as a safety measure against an explosive polyaddition of alkylene oxides.

In embodiments where more than one alkylene oxide is desired to be introduced into the polyether side chains of modified polypropyleneimine (B), the various alkylene oxide units may be randomly distributed or blocky. If several alkylene oxides are introduced simultaneously into the reaction, deviations from the strict random principle during incorporation of the alkylene oxide units can result from different alkylene oxides having a different reactivity. It is possible to achieve a predetermined incorporation of the alkylene oxide units by means of a programmed feed of the alkylene oxides. If the alkylene oxides are fed in successively, a block-like distribution of the alkylene oxide units is generally obtained.

The alkoxylation may preferably be carried out in two or more substeps, the first step being to first to analkoxylate polypropyleneimine. Below is meant were standing, that one brings polypropyleneimine with a molar number of alkylene oxide to the reaction, which corresponds to the number of primary and secondary amino groups in the respective polypropyleneimine. The alkoxylation is preferably carried out in aqueous solution and without catalyst.

In one embodiment of the present invention, it is possible to carry out the alkoxylation at a reaction temperature in the range from 70 to 200 ° C., preferably in the range from 80 to 160 ° C. In one embodiment of the present invention, it is possible to carry out the alkoxylation at a pressure of up to 10 bar, preferably up to 8 bar. The lower limit is normal pressure.

In the second sub-step - and optionally in further substeps - alkoxylated then with more alkylene oxide. This further alkoxylation is carried out in the presence of catalyst. Suitable catalysts are mentioned above.

The second substep-and optionally the further substeps-can be carried out in each case in bulk, embodiment (i), or in an organic solvent, embodiment (ii). For carrying out embodiment (i), the water can be removed from the partial step, preferably before the addition of a water-sensitive catalyst. The water can be distilled off, for example, by heating to a temperature in the range of 80 to 150 ° C at a reduced pressure in the range of 0.01 to 0.5 bar. If the catalyst is insensitive to water, for example alkali metal hydroxide, it is also possible first to add the catalyst and then to remove the water.

In one embodiment of the present invention, the further alkoxylation can be carried out at a reaction temperature in the range from 70 to 200 ° C., preferably in the range from 100 to 180 ° C.

In one embodiment of the present invention, further alkoxylation can be carried out at a pressure of up to 10 bar, preferably up to 8 bar. The lower limit is normal pressure. In one embodiment of the present invention, the further alkoxylation is carried out over a period of 30 minutes to 12 hours.

Examples of suitable solvents for carrying out embodiment (ii) are nonpolar and polar aprotic organic solvents. Examples of particularly suitable nonpolar aprotic organic solvents are aliphatic and aromatic hydrocarbons such as n-hexane, n-heptane, cyclohexane, toluene and the various isomers of xylene. Examples of particularly suitable polar aprotic solvents are ethers, in particular Other cyclic ethers such as tetrahydrofuran and 1, 4-dioxane, further Ν, Ν-dialkylamides such as dimethylformamide and dimethylacetamide and N-alkyl lactams such as N-methylpyrrolidone and N-ethylpyrrolidone. It is also possible to use mixtures of two or more of the aforementioned solvents. Particularly preferred solvents are xylene, especially as a mixture of isomers, and toluene.

It is also advantageous for embodiment (ii) to remove any water originating from the sub-step of the alkoxylation, preferably even before the addition of the catalyst, for example at a temperature in the range from 120 to 180 ° C. and at reduced temperature Pressure, for example, 0.01 to 0.5 bar, or by stripping with nitrogen. After addition of the solvent, the further alkoxylation then takes place as in the second and, if appropriate, further substeps of embodiment (ii). Before further processing, remove the organic solvent (s). Polypropyleneimine (B), which may be alkoxylated, may have as counter ions high molecular weight or low molecular weight anions, organic or preferably inorganic. High molecular weight anions in the context of the present invention have an average molecular weight of 200 g / mol or more, for example up to 2500 g / mol, low molecular weight anions have a molecular weight of less than 200 g / mol, for example from 17 to 150 g / mol. Examples of low molecular weight organic counterions are acetate, propionate and benzoate. Examples of low molecular weight inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate and bicarbonate.

In one embodiment of the present invention, modified polypropylenimine (B) has a cationic charge density of at least 5 meq / g to preferably at most 25 meq / g (milliequivalents / g), preferably to 22 meq / g, with the indication in g being modified Polypropyleneimine (B) without consideration of the counterions relates. The cationic charge density can be determined, for example, by titration, for example with polyvinyl sulfate solution.

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

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

total in the range of 1 to 50% by weight of aminocarboxylate (A), preferably 10 to 25% by weight, in total in the range of 0.001 to 5% by weight of polypropyleneimine (B), which may be alkoxylated, preferably 0.02 to 0.5 wt .-%, each based on solids content of the formulation in question. In a variant of the present invention formulation according to the invention contains compound (A) and polypropyleneimine (B), which may be alkoxylated, in a weight ratio in the range from 1000 to 1 to 25 to 1. In a preferred embodiment of the present invention formulation according to the invention is free from Phosphates and polyphosphates, wherein hydrogen phosphates are subsumed with, for example, free of trisodium phosphate, pentasodium tripolyphosphate and Hexanatri- ummetaphosphat. 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 formulations according to the invention comprise at least one zinc salt. Zinc salts can be selected from water-soluble and non-water-soluble zinc salts. For the purposes of the present invention, zinc salts which are not water-soluble and which have a solubility of 0.1 g / l or less in distilled water at 25 ° C. Accordingly, zinc salts which have a higher water solubility are referred to in the context of the present invention as water-soluble zinc salts.

In one embodiment of the present invention, zinc salt is selected from zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnC, ZnS0 ₄ , zinc acetate, zinc nitrate, Zn (NOs) 2,

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

In another embodiment of the present invention, zinc salt is selected from ZnO, ZnOaq, Zn (OH) 2 and ZnCO-3. ZnOaq is preferred.

In one embodiment of the present invention, zinc salt is selected from zinc oxides having an average particle diameter (weight average) in the range of 10 nm to 100 μm.

The cation in zinc salt can be complexed, for example, complexed with ammonia ligands or water ligands, and in particular be present hydrated. To simplify the notation, ligands are generally omitted in the context of the present invention, if they are water ligands.

Depending on how to adjust the pH of mixture according to the invention, zinc salt can be converted. It is thus possible, for example, to use zinc acetate or ZnC for the preparation of the formulation according to the invention, but this converts to ZnO, Zn (OH) 2 or ZnOaq at a pH of 8 or 9 in an aqueous environment, which in non-complexed or may be in complexed form. Zinc salt is present in such inventive formulations, which are solid at room temperature, preferably in the form of particles, for example, have a mean diameter (number average) in the range of 10 nm to 100 μηη, preferably 100 nm to 5 μηη, determined for example by X-ray scattering.

Zinc salt is present in such inventive formulations, which are liquid at room temperature, in dissolved or solid or in colloidal form.

In one embodiment of the present invention, formulations according to the invention contain in total from 0.05 to 0.4% by weight of zinc salt, based in each case on the solids content of the relevant formulation.

The proportion of zinc salt is given as zinc or zinc ions. Thus one can calculate out the portion of the Gegenions.

In one embodiment of the present invention, formulations according to the invention are heavy-metal-free, with the exception of zinc compounds. For the purposes of the present invention, this is understood to mean that formulations according to the invention are free of those heavy metal compounds which do not act 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 and based on In addition to zinc, the formulation according to the invention preferably has a heavy metal content of less than 0.05 ppm, based on the solids content of the relevant formulation, ie the proportion of zinc is not included.

As "heavy metals" all metals are in the context of the present invention having a specific density of at least 6 g / cm ³ with the exception of zinc. In particular, considered as heavy metals, precious metals and bismuth, iron, copper, lead, tin, nickel, cadmium and chromium ,

Preferably, formulation according to the invention contains no measurable proportions of bismuth compounds, that is to say, for example, less than 1 ppm.

Formulations of the invention may contain other components which are advantageous, for example, for use in washing dishes and / or kitchen utensils.

In another embodiment of the present invention, formulations according to the invention contain no further components which are suitable, for example, for use in the

Rinsing dishes and / or kitchen utensils are advantageous, but can be easily formulated with other components and are therefore suitable as a starting material. In one embodiment of the present invention formulations according to the invention contain sodium citrate (C). The term sodium citrate comprises the mono- and preferably the disodium salt with. Sodium citrate can be used as anhydrous salt or as a hydrate, for example as a dihydrate.

(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 persulphate, where the term "persulphate" in each case the salt of peracid H2SO5 and the Peroxodisulfate includes.

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

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

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

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

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

In one embodiment of the present invention, the formulation according to the invention contains from 0.1 to 10% by weight of water, based on the sum of all solids of the relevant formulation.

In one embodiment of the present invention, formulation according to the invention may comprise further ingredients (E), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more several bleaches, one or more bleach catalysts, one or more bleach activators, one or more bleach stains, bilisators, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more fragrances, one or more organic solvents, one or more tabletting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizers.

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

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

in which the variables are defined as follows: identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl, selected from C 5 -C 22 -alkyl, for example nC & Hn, n-doF i, n- Ci2H25, nC-uF s), n-Ci6H33 selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or iso- Decyl, m and n range from zero to 300, with the sum of n and m being at least one. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

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

Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II) in which the variables are defined as follows: R ^{1 is} identical or different and selected from linear C ¹ -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,

R ^{4 is} selected from C 6 -C 20 -alkyl, in particular n-CsH-i, n-doH-i, n-C 12 H 25, nC-uF s), n-C 16 H 33, n

a is a number in the range of 1 to 6,

b is a number in the range of 4 to 20, d is a number in the range of 4 to 25.

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

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

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

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

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

Formulations according to the invention may contain, for example, up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, in each case based on the total solids content of the formulation according to the invention. Formulations according to the invention may comprise, in addition to sodium citrate (C), one or more builders, in particular phosphate-free builders. Examples of suitable builders are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the formula a-Na 2 Si 2 O, β-Na 2 Si 2 O, and 5-Na 2 Si 2 O, furthermore fatty acid sulfonates, α-hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl- and alkenyl disuccina tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders such as polycarboxylates and polyaspartic acid.

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

(Meth) acrylic acid copolymers.

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

It is also possible copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C3-Cio-mono- or C4-Cio-dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid with at least one hydrophilic or hydrophobically modified monomers as enumerated below.

Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 - Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C22-α-olefin, a mixture of C2o-C24-α-olefins and polyisobutene having an average of 12 to 100 carbon atoms per molecule.

Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy functionality 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 monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2- hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-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 vinylphosphonic acid and its salts.

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

Formulations according to the invention may contain, for example, in the range from 10 to 50% by weight, preferably up to 20% by weight, of builder.

In one embodiment of the present invention, formulations according to the invention may contain one or more co-builders. Examples of cobuilders are phosphonates, for example hydroxyalkanephosphonates and aminoalkanephosphonates. Among the hydroxyalkane phosphonates, the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. Formulations of the invention may contain one or more alkali carriers. Alkaline carriers, for example, provide the pH of at least 9 when an alkaline pH is desired. Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates. Preferred alkali metal is in each case potassium, particularly preferred is sodium.

Formulations according to the invention may contain, in addition to bleaching agent (D), one or more chlorine-containing bleaching agents.

Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate. For example, formulations according to the invention may contain in the range of from 3 to 10% by weight of chlorine-containing bleach.

Formulations of the invention may contain one or more bleach catalysts. Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands 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-dioxohexahydro -1, 3,5-triazine ("DADHT") or nitrile quats (trimethylammonium acetonitrile salts).

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

Formulations of the invention may contain one or more corrosion inhibitors. This is to be understood in the present case, such compounds that inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

In one embodiment of the present invention formulations according to the invention contain a total of in the range of 0.1 to 1, 5 wt .-% corrosion inhibitor.

Formulations of the invention may contain one or more builders, for example, sodium sulfate.

Formulations according to the invention may contain one or more defoamers, selected for example from silicone oils and paraffin oils.

In one embodiment of the present invention, formulations according to the invention contain in total in the range from 0.05 to 0.5% by weight defoamer. Formulations according to the invention may contain phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid. Another object of the present invention is the use of formulations according to the invention for the automatic cleaning of dishes and kitchen utensils. As kitchen utensils in the context of the present invention, for example, pots, pans, casseroles to call, and metal objects such as, for example, skimmers, roasters and garlic presses.

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

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.

For rinsing, water with a hardness in the range of 1 to 30 ° dH, preferably 2 to 25 ° dH, may also be used.

If machine-cleaning formulations according to the invention are used, even with repeated mechanical cleaning of objects which have at least one surface made of glass, there is very little tendency for glass corrosion, even if objects comprising at least one surface made of glass are used have, along with heavily soiled cutlery or dishes cleans. In addition, it is much less harmful to use the formulation according to the invention in order to mix glass together with articles. To clean the metal, for example, together with 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, in short also called production process according to the invention. For carrying out the preparation process according to the invention, it is possible, for example, to proceed in such a way that

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

(B) at least one polypropyleneimine which may be alkoxylated,

and optionally

(C) sodium citrate or

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

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

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

In one embodiment of the present invention, before at least partially removing the water, one may mix with one or more other ingredients (E) for formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more builders, one or more builders several co-builders, in particular phosphorus-free builders, one or more alkali carriers, one or more bleaches, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders , with buffer or dye.

In one embodiment, the water is completely or partially removed, for example, to a residual moisture in the range from 0.1 to 10% by weight of the formulation according to the invention by evaporation, in particular by spray drying, spray granulation or compaction.

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

Another object of the present invention are modified polypropyleneimines (B), prepared by alkoxylation of polypropyleneimine, which is prepared by transamination of propanediamine and optionally up to 40 mol% of at least one other aliphatic diamines. Preparation and properties of modified polypropyleneimines (B) according to the invention are described above.

The invention is illustrated by working examples. General: Care was taken that after the first cleaning of the specimens in the household dishwasher until after weighing and visual patterning of the glasses, the specimens were only touched with clean cotton gloves, so that the weight or the visual impression of the specimens was not falsified. Data in% are wt .-%, unless expressly stated otherwise. Data in ° dH always relate to the permanent hardness.

I. Preparation of alkoxylated polypropyleneimines

1.1 Production of Polypropylene Imines

1.1.1 Preparation of linear polypropyleneimine L-PPI.1

200 ml of 1, 3-propanediamine ("1, 3-PDA") were introduced into a 300 ml steel vessel connected to a tubular reactor with an internal diameter of 27 mm. PDA together with 50 Nl of hydrogen passed through a fixed bed Ni / Co catalyst supported on ZrO2 in the tube reactor at a reaction temperature of 160 ° C. At the top of the tube reactor, gas and liquid phase were separated and the liquid portion was introduced into the steel vessel From there, it was pumped back over the catalyst and the reaction was carried out for 2 hours to give L-PPI.1 whose properties are listed in Table 1.

1.1.2 Preparation of Linear Polypropyleneimine L-PPI.2 200 ml of 1, 3-propanediamine ("1, 3-PDA") were introduced into a 300 ml steel vessel connected to a tubular reactor with an internal diameter of 27 mm. PDA together with 50 Nl of hydrogen passed through a fixed bed Ni / Co catalyst supported on ZrO2 in the tube reactor at a reaction temperature of 160 ° C. At the top of the tube reactor, gas and liquid phase were separated and the liquid portion was introduced into the steel vessel From there, it was pumped back over the catalyst and the reaction was carried out for 150 minutes to give L-PPI.2, whose properties are listed in Table 1. 1.1.3 Preparation of Linear Polypropyleneimine L-PPI.3

One repeated the reaction of 1.1.2, but only over a period of 90 minutes. This gave L-PPI.3. 1.1.4 Preparation of linear polypropyleneimine L-PPI.4

A tubular reactor with an internal diameter of 27 mm was used to continuously conduct 1, 3-PDA, together with 10 standard liters / h of hydrogen, over a cobalt-fixed bed catalyst. The total pressure was 50 bar, the temperature 170 ° C. The intake of 1, 3-PDA was 0.8 kg / L _ca fh. A crude product was obtained. Unreacted 1, 3-PDA and the corresponding dimer and trimer were distilled off from the crude product and gave L-PPI.4 as a colorless liquid.

1.1.5 Preparation of linear polypropyleneimine L-PPI.5 A tubular reactor with an internal diameter of 27 mm was used to continuously conduct 1, 3-PDA, together with 10 standard liters / h of hydrogen, over a cobalt fixed-bed catalyst. The total pressure was 50 bar, the temperature 160 ° C. The intake of 1, 3-PDA was 0.8 kg / L _ca fh. A crude product was obtained. Unreacted 1, 3-PDA and the corresponding dimer and trimer were distilled off from the crude product and gave L-PPI.5 as a colorless liquid.

1.1.6 Preparation of linear polypropyleneimine L-PPI.6

A tubular reactor with an internal diameter of 27 mm was used to continuously conduct 1, 3-PDA, together with 10 standard liters / h of hydrogen, over a cobalt-fixed bed catalyst. The total pressure was 50 bar, the temperature 160 ° C. The intake of 1, 3-PDA was 0.6 kg / L _ca fh. A crude product was obtained which, according to gas chromatography, had 7% by weight unreacted 1,3-PDA. Distilled 1, 3-PDA and the corresponding dimer and trimer and received L-PPI.6 as a colorless liquid.

M _n : 302 g / mol, M _w : 533 g / mol: M _w / M _n of 1.8. Table 1: Linear polypropyleneimines and their properties

Primary and secondary amine numbers are given in mg KOH / g.

PAZ: primary amine number

SAZ: Secondary amine number

I.2 Alkoxylation of Polypropyleneimine

1.2.1 Alkoxylation with a molar ratio EO / NH of 1: 1 A 2 liter autoclave is charged with 286.3 g of polypropyleneimine L-PPI.1 (tertiary amine number: 22.1 mg KOH / g) and 14.3 g of water. The autoclave was flushed with nitrogen three times and then heated to 1 10 ° C. Within 2 hours, 265.2 g of ethylene oxide were added. To complete the reaction, it was stirred at 110 ° C. for 3 hours. Thereafter, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 ° C. This gave alkoxylated polypropyleneimine (B.1) according to the invention as a highly viscous yellow oil (522 g).

1.2.2 Alkoxylation with a molar ratio EO / NH of 10: 1 In a 2 liter autoclave, 75.9 g (B.1) and 2.6 g KOH pellets (water content: 50% by weight) are introduced , The mixture was heated with stirring under reduced pressure (10 mbar) to 120 ° C and stirred for 2 hours to remove the water. Thereafter, the autoclave was purged three times with nitrogen and then heated to 140 ° C (1 bar). Within 2 hours, 332.8 g of ethylene oxide were added. To complete the reaction, it was stirred at 140 ° C over a period of 3 hours. Thereafter, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 ° C. This gave inventive alkoxylated polypropyleneimine (B.2) as a yellow waxy solid (399.5 g).

1.2.3 Alkoxylation with a molar ratio EO / NH of 20: 1

64.0 g (B.1) and 2.6 g KOH cookies (water content: 50% by weight) are placed in a 2 liter autoclave. The mixture was heated with stirring under reduced pressure (10 mbar) to 120 ° C and stirred for 2 hours to remove the water. Thereafter, the autoclave was purged three times with nitrogen and then heated to 140 ° C (1 bar). Within 4 hours, 584.7 g of ethylene oxide were added. To complete the reaction, it was stirred for a period of 3 Hours at 140 ° C. Thereafter, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 ° C. This gave alkoxylated polypropyleneimine (B.3) according to the invention as a yellow waxy solid (630.6 g). Amine number: 57.2 mg KOH / g. I.2.4 Alkoxylation with a molar ratio EO / PO / NH of 10: 7: 1

225.6 g (B.2) and 0.8 g KOH biscuits (water content: 50% by weight) are placed in a 2 liter autoclave. The mixture was heated with stirring under reduced pressure (10 mbar) to 120 ° C and stirred for 2 hours to remove the water. Thereafter, the autoclave was purged three times with nitrogen and then heated to 140 ° C (1 bar). Within 2 hours, 187.9 g of propylene oxide were added. To complete the reaction, it was stirred at 140 ° C over a period of 3 hours. Thereafter, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 ° C. This gave inventive alkoxylated polypropyleneimine (B.2) as a pale yellow waxy solid (405 g). Amine number: 58.3 mg KOH / g.

1.2.5 Alkoxylation with a molar ratio EO / PO / NH of 24: 16: 1

In a 2 liter autoclave, 242.8 g (B.3) and 1.1 g KOH pellets (water content: 50% by weight) are introduced. The mixture was heated with stirring under reduced pressure (10 mbar) to 120 ° C and stirred for 2 hours to remove the water. Thereafter, the autoclave was purged three times with nitrogen and then heated to 140 ° C (1 bar). 46.1 g of ethylene oxide were added and allowed to react with stirring for three hours. Then, within 2 hours, 242.9 g of propylene oxide were added. To complete the reaction, the mixture was stirred at 140 ° C over a period of 3 hours. Thereafter, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 ° C. This gave alkoxylated polypropyleneimine (B.5) according to the invention as a light brown solid (506 g). Amine number: 28.6 mg KOH / g.

1.2.6 Alkoxylation with a molar ratio BuO / NH of 1: 1

193.7 g of polypropyleneimine L-PPI.1 and 9.7 g of water are placed in a 2-liter autoclave. The autoclave was flushed with nitrogen three times and then heated to 1 10 ° C. Within 2 hours, 293.6 g of 1,2-butylene oxide were added. To complete the reaction, it was stirred at 110 ° C. for 3 hours. Thereafter, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 ° C. This gave alkoxylated polypropyleneimine (B.6) according to the invention as a highly viscous yellow oil (460 g).

1.2.7 Alkoxylation with a molar ratio EO / NH of 4: 1 In a 2 liter autoclave, 151, 8 g (B.1) and 2.6 g KOH pellets (water content: 50% by weight) are introduced , The mixture was heated with stirring under reduced pressure (10 mbar) to 120 ° C and stirred for 2 hours to remove the water. Thereafter, the autoclave was washed three times Nitrogen and then heated to 140 ° C (1 bar). Within 2 hours, 265.6 g of ethylene oxide were added. To complete the reaction, it was stirred at 140 ° C over a period of 3 hours. Thereafter, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 ° C. This gave inventive alkoxylated polypropyleneimine (B.7) as a yellow waxy solid.

I.2.8 Alkoxylation with a molar ratio EO / NH of 7: 1

In a 2 liter autoclave, 151, 8 g (B.1) and 2.6 g KOH cookies (water content: 50% by weight) are introduced. The mixture was heated with stirring under reduced pressure (10 mbar) to 120 ° C and stirred for 2 hours to remove the water. Thereafter, the autoclave was purged three times with nitrogen and then heated to 140 ° C (1 bar). Within 2 hours, 463.8 g of ethylene oxide were added. To complete the reaction, it was stirred at 140 ° C over a period of 3 hours. Thereafter, water and remaining volatile compounds, if present, were removed in vacuo (10 mbar) at 90 ° C. This gave inventive alkoxylated polypropyleneimine (B.8) as a yellow solid.

If, instead of L-PPI.1, the linear polypropyleneimine L-PPI.4 is used and reacted with appropriate amounts of ethylene oxide, the alkoxylated polypropyleneimines M-PPI.4-1 to M-PPI.4-3 according to the invention are obtained ,

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

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

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

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

11.1 Production of basic mixtures First, base mixtures were prepared from the starting materials according to Table 2. The starting materials were mixed dry.

Table 2: Basic mixtures for experiments with formulations according to the invention and comparative formulations

All information in g. (C.1) is determined as anhydrous sodium citrate.

Abbreviations:

MGDA: methylglycine diacetic acid as trisodium salt

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

II.2 Preparation of formulations according to the invention

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

Polypropyleneimines (B) and modified polypropyleneimines (B) according to Table 3 were used.

Table 3: Modified polypropyleneimines

Action: In a 100 ml beaker, 20 ml of distilled water were added and modified polypropylenimine (B) or polypropyleneimine (B) according to Tables 3 and 4 were added with stirring.

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

By dosing in the test the appropriate proportions of the base mixture separately from the aqueous solution of (A.1), (B), sodium citrate (C.1) or (D.1), the same results were obtained as when the dried formulation was mixed with tested equal amounts of active ingredients. So it does not depend on the order of the dosage.

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

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

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

111.1 Test method Dishwasher with endurance runner

Dishwasher: Miele G 1222 SCL

Program: 65 ° C (with pre-rinse)

Washware: 3 champagne glasses "GILDE", 3 shot glasses, "INTERMEZZO" For cleaning, the glasses were placed in the upper dish rack of the dishwasher. The dishwashing agent used was in each case 25 g of formulation according to the invention or 25 g of comparison formulation according to Table 4, wherein Table 4 individually specifies the active components (A.1), base mixture and (B) of formulation according to the invention. Rinsing was carried out at a rinse temperature of 55 ° C. The water hardness was in each case in the range of zero to 2 ° dH. One rinsed 100 rinse cycles each, i.e., the program was run 100 times. The evaluation was carried out gravimetrically and visually after 100 rinsing cycles.

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

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

Experimental procedure:

First, they rinsed for the purpose of pretreatment, the test pieces in a domestic dishwashing machine (Bosch SGS5602) with 1 g of surfactant (n-Ci8H37 (OCH ₂ CH 2) ioOH) and 20 g of citric acid, to remove any impurities. The test pieces were dried, their weight determined and fixed on the grid floor insert.

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

The assessments were made according to the following scheme.

Line corrosion:

L5: no lines to recognize

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

L3: line corrosion in some areas

L2: line corrosion in several areas

L1: Strong line corrosion. Glass opacity

L5: no haze visible

L4: low turbidity in very few areas

L3: cloudiness in some areas

L2: cloudiness in several areas

L1: markedly turbid over almost the entire glass surface

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

When using water at 2 ° dH 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.

III.2 Results

The results are summarized in Table 4. Table 4: Results of tests with dishwasher (endurance runner)

When using formulations according to the invention, only little or no glass corrosion was always found.

Claims

claims

Formulation containing

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

(B) at least one polypropyleneimine which may be alkoxylated.

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

Formulation according to Claim 1 or 2, characterized in that polypropyleneimine (B) is selected from polypropyleneimines which are reacted with ethylene oxide or propylene oxide.

A formulation according to any one of claims 1 to 3, characterized in that it contains at least one zinc salt.

A formulation according to any one of claims 1 to 4, characterized in that polypropyleneimine (B) is selected from linear polypropyleneimines which may be alkoxylated.

A formulation according to any one of claims 1 to 5, characterized in that, apart from zinc, it has a heavy metal content below 0.05 ppm, based on the solids content of the relevant formulation.

A formulation according to any one of claims 1 to 6, characterized in that it contains in the range of 0.1 to 10 wt .-% water.

A formulation according to any one of claims 1 to 7, characterized in that the molar ratio of nitrogen atoms to alkylene oxide groups in alkoxylated polypropyleneimine (B) is in the range of 1: 1 to 1:15.

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

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

in the range of 0.001 to 2% by weight of optionally alkoxylated polypropyleneimine (B),

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

Use of formulations according to any one of claims 1 to 9 for rinsing dishes and utensils while rinsing with water having a hardness of 2 to 25 ° dH.

1 1. Use of formulations according to any one of claims 1 to 9 for rinsing articles having at least one surface of glass which may be decorated or not decorated.

12. Use according to claim 10 or 1 1, characterized in that the rinsing is a rinsing with a dishwasher.

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

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

characterized in that one

(B) at least one polypropyleneimine which may be alkoxylated,

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

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