KR20150013590A - Formulations, use thereof as or for production of dishwashing detergents and production thereof - Google Patents

Abstract

The present invention relates to formulations containing:
(A) at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), salts and derivatives thereof, and
(B) at least one alkylene imine polymer covalently modified with at least one carboxylic acid or at least one derivative of at least one carboxylic acid or at least one derivative of a carboxylic acid, wherein the primary and secondary Up to 75 mole% of the nitrogen atoms of the amino group are reacted with the carboxylic acid or carboxylic acid or derivatives of the carboxylic acid).

Description

FORMULATIONS, USE THEREOF AS OR FOR PRODUCTION OF DISHWASHING DETERGENTS AND PRODUCTION THEREOF FIELD OF THE INVENTION [0001]

The present invention relates to formulations containing:

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

(B) at least one alkyleneimine polymer covalently modified with at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of a carboxylic acid, wherein the nitrogen of the primary and secondary amino groups of the alkyleneimine polymer Up to 75 mole% of the atoms react with carboxylic acids or carboxylic acid or derivatives of carboxylic acids.

Furthermore, the invention relates to a process for the preparation of the formulations according to the invention, and to dishwashing compositions, in particular as dishwashing appliance compositions for dishwashing or for their use.

The dishwashing composition must meet a number of requirements. Therefore, they must basically clean the dishes, they should not have harmful or potentially harmful substances in the wastewater, and they must allow the spilling and drying of water from the dishes, and they should not cause problems during the operation of the dishwasher. Finally, they should not result in aesthetically undesirable effects on the product you want to clean. In this regard, glass corrosion is particularly mentioned.

Glass corrosion occurs not only as a result of mechanical effects of, for example, friction between glasses, or mechanical contact between glass and parts of a dishwasher, but also by chemical effects. For example, certain ions can dissolve out of the glass through repetitive machine cleaning, which changes the optical properties and thus the aesthetic properties in a negative way.

In the case of glass corrosion, various effects are observed. First, microscopic microscopic crack formation can be observed, which is recognizable in the form of lines. Second, in most cases, general opacity, e.g., roughness, can be observed, which indicates that the glass is not attractive. In addition, this type of influence is subdivided into synthetically irregular discoloration, formation of ridges, and also sheet and annular opacity.

From WO 2002/64719 it is known that certain copolymers of ethylenically unsaturated carboxylic acids with esters of, for example, ethylenically unsaturated carboxylic acids can be used in the dishwashing compositions.

WO 2006/108857 relates to alkoxylated polyethyleneimines as additives to detergents. For example, detergents containing zeolites or polyaminocarboxylates such as EDTA or triethylenediamine pentaacetate as complexing agents are disclosed.

WO 01/96516 proposes formulations containing alkoxylated polyethyleneimines for hard surface cleaning. Purified water is used for rinsing.

WO 2010/020765 describes a dishwashing composition comprising polyethyleneimine. This type of dishwashing composition may comprise phosphate or may not contain phosphate. They are characterized by good inhibition of glass corrosion. Zinc-and-bismuth-containing dishwashing compositions.

It is therefore an object to provide a formulation suitable as a dishwashing composition which avoids known drawbacks in the prior art and prevents or at least significantly reduces glass corrosion. It is also an object to provide a process for the preparation of a formulation which is suitable as a dishwashing composition or for its preparation and avoids the known drawbacks of the prior art. It is also an object to provide the use of formulations.

Thus, the formulations defined in the introduction are also abbreviated as formulations of the present invention.

Formulations according to the present invention comprise:

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

The compound (A) is preferably selected as the liberated acid, particularly preferably the completely or partially neutralized form, i.e. the salt. Suitable counter ions include, for example, inorganic cations such as ammonium, alkali or alkaline earth metals, preferably Mg ²⁺ , Ca ²⁺ , Na ⁺ , K ⁺ , or organic cations, preferably one or more organic radicals substituted ammonium, in particular triethanol ammonium, N, N- di-ethanol ammonium, N- mono- -C ₁ -C ₄ - alkyl diethanol ammonium, for example, N- methyl diethanol ammonium or Nn- butyl diethanol ammonium, and N , N-di-C ₁ -C ₄ -alkylethanolammonium.

Very particularly preferred compounds (A) are alkali metal salts, especially sodium salts, of methyl glycine diacetate (MGDA), iminosuccinic acid (IDA) and glutamic acid diacetate (GLDA).

Very particularly preferably, methylglycine diacetate (MGDA), iminosuccinic acid (IDA) or glutamic acid diacetate (GLDA) are completely neutralized.

Furthermore, the formulations according to the invention comprise:

(B) at least one alkyleneimine polymer covalently modified with at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of a carboxylic acid, also referred to as a shortened polyalkyleneimine (B) Wherein up to 75 mole percent of the nitrogen atoms of the primary and secondary amino groups of the alkylene imine polymer react with the carboxylic or carboxylic acid or derivatives of the carboxylic acid.

In the context of the present invention, alkylene imine polymers are understood to mean polymeric materials obtained by single- or copolymerization of one or more cyclic imines, or by grafting with one or more imines of (co) polymers. Polyalkylene polyamines grafted with ethyleneimine and polyimidoamines are exemplified.

In the context of the present invention, the polyalkylene polyamines preferably contain at least 6 nitrogen atoms per molecule and at least 5 C ₂ -C ₁₀ -alkylene units, preferably C ₂ -C ₃ -alkylene units Is understood to mean a polymer, for example, pentaethylene hexamine, especially polyethyleneimine.

Polyalkylene polyamines and in particular polyethyleneimines can have, for example, an average molecular weight (Mw) of at least 300 g / mol; Preferably, the average molecular weight of the alkylene imine polymer as measured by gel permeation chromatography (GPC) is in the range of 500 to 1,000,000 g / mol, particularly preferably 800 to 25,000 g / mol.

The polyalkylene polyamine may be covalently modified as an alkylene imine polymer in a partially quaternized (alkylated) form. Suitable quaternizing agents (alkylating agents) are, for example, alkyl halides, especially C ₁ -C ₁₀ -alkyl chlorides such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, , tert-butyl chloride, n-hexyl chloride, also epichlorohydrin, dimethyl sulfate, diethyl sulfate and benzyl chloride. If the quaternized (alkylated) polyalkylene polyamine as the alkylene imine polymer is covalently modified, the quaternization (alkylation) or conversion of the quaternized (alkylated) polyamine to the quaternized 1 to 25, particularly preferably not more than 20 mol%.

Furthermore, polyalkylene polyamines and especially polyethyleneimines can be covalently modified as alkylene imine polymers in a partially C ₂ -C ₂₂ -epoxide-alkoxylated form. Examples of suitable C ₂ -C ₂₂ -epoxides are ethylene oxide, propylene oxide, n-hexylene oxide, and styrene oxide. When the partially alkoxylated polyalkylene polyamine is modified covalently with C ₂ -C ₂₂ -epoxide as the alkylene imine polymer, the degree of alkoxylation is preferably determined by the amount of alkoxylatable N 1 to 25, particularly preferably not more than 20 mol%, based on the atoms.

Furthermore, polyimidoamines grafted with ethyleneimine are suitable as alkyleneimine polymers. Suitable polyamidoamines are obtainable, for example, by reacting a C ₄ -C ₁₀ -dicarboxylic acid with a polyalkylene polyamine preferably containing from 3 to 10 basic nitrogen atoms in the molecule. Suitable dicarboxylic acids are, for example, succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is also possible to use a mixture of the above-mentioned dicarboxylic acids, for example, a mixture of adipic acid and glutaric acid or a mixture of maleic acid and adipic acid. It is preferable to use adipic acid for the production of polyamicamines. Suitable polyalkylene polyamines to be condensed with the above-mentioned dicarboxylic acids are, for example, diethylene triamine, triethylene tetramine, dipropylene triamine, tripropylene tetramine, dihexamethylene triamine, Bis-aminopropylethylenediamine. The above-mentioned polyalkylene polyamines can be used in the form of a mixture in the preparation of polyamidoamines. The preparation of the polyamidoamine preferably takes place without dilution, but may optionally be carried out in an inert solvent. Condensation with polyalkylene polyamines of dicarboxylic acids takes place at elevated temperatures, for example in the range of 120 to 220 占 폚. The water formed during the reaction is distilled off from the reaction mixture. Condensation may be carried out in the presence of a lactone or lactam of a carboxylic acid optionally having 4 to 8 carbon atoms. Generally, 0.8 to 1.4 moles of polyalkylene polyamine per mole of dicarboxylic acid is used. Polyamideamines obtainable in such a way have primary and secondary NH groups and are water-soluble.

Polyimidoamines grafted with ethyleneimine can be prepared by allowing ethyleneimine to act on the polyamidoamine phase described above in the presence of Bronsted acid or Lewis acid, such as sulfuric acid, phosphoric acid or boron trifluoride etherate have. As a result, the ethyleneimine is grafted onto the polyamidoamine of interest. For example, from 1 to 10 ethylene imine units can be grafted per basic nitrogen atom in the polyamidoamine, i.e. about 10 to 500 parts by weight of ethyleneimine is used for 100 parts by weight of polyamidoamine.

A preferred alkylene imine polymer is polyethyleneimine.

In one embodiment of the invention, the average molecular weight Mw of the polyethyleneimine is in the range of 500 to 1,000,000 g / mol, preferably in the range of 600 to 75,000 g / mol, as measured by gel permeation chromatography (GPC) Particularly preferably 800 to 25,000 g / mol.

In one embodiment of the invention, the polyethyleneimine is selected from highly branched polyethyleneimines. Highly branched polyethyleneimines are characterized by their high degree of branching (DB). The degree of branching is determined, for example, by a ¹³ C-NMR spectrometer, preferably in D ₂ O, and is determined as follows:

DB = D + T / D + T + L

(Wherein D (dendritic) corresponds to the fraction of the tertiary amino group, L (linear) corresponds to the fraction of the secondary amino group, and T (terminal) corresponds to the fraction of the primary amino group).

In the context of the present invention, the highly branched polyethyleneimine is a polyethyleneimine having DB in the range of 0.1 to 0.95, preferably in the range of 0.25 to 0.90, particularly preferably in the range of 0.30 to 0.80%, and very particularly preferably 0.5 or more.

In one embodiment of the present invention, polyethyleneimine is an average molecular weight M _w of 600 to 75 000 g / mol range, preferably from 800 to 25 000 g / mol in mounds branching polyethyleneimine (homopolymer), a range of .

In the context of the present invention, the alkylene imine polymer is used in a covalently modified form, specifically a total of up to 75 mole% of the nitrogen atoms of the primary and secondary amino groups of the alkylene imine polymer, To 60 mole percent of the at least one carboxylic acid or carboxylic acid or at least one derivative of the carboxylic acid. Thus, in the context of the present invention, the reaction (formula) can be, for example, alkylation or amination.

In one embodiment of the invention, the modified polyalkyleneimine (B) is selected from alkylene imine polymers, and in particular is a polyethyleneimine as follows:

(B1) reacted with one or more ethylenically unsaturated C ₃ -C ₁₀ carboxylic acids, or

(B2) is reacted with at least one C ₅ -C ₁₂ -carboxylic acid, free of ethylene double bonds,

(B3) reacted with at least one carboxylic acid ester,

(B4) For example, in the context of Strecker synthesis, reacted with hydrocyanic acid and formaldehyde.

Examples of ethylenically unsaturated C ₃ -C ₁₀ -carboxylic acids are fatty acids, preferably α, β-ethylenically unsaturated C ₃ -C ₁₀ -carboxylic acids, for example (E) - or (Z) Methacrylic acid and especially acrylic acid. As a result of the reaction with the carboxylic acid _{(s), C 3 -C 10 - -} C 3 -C 10 carboxylic acid (s), preferably a group in the context of the Michael addition, of an alkylene imine polymer derived from NH ₂ Or a nitrogen atom derived from an NH group.

Examples of C ₅ -C ₁₂ -carboxylic acids without ethylene double bonds are valeric acid, capric acid, caprylic acid, n-octanoic acid, n-decanoic acid and lauric acid. As a result of the reaction with the C ₅ -C ₁₂ -carboxylic acid (s) having no ethylene double bond, amidation of the nitrogen atom derived from the NH 2 group or the NH group is preferably carried out.

Examples of derivatives of C ₅ -C ₁₂ -carboxylic acids without ethylene double bonds are esters thereof, for example C ₁ -C ₄ -alkyl esters, in particular ethyl and methyl esters. Examples are methylvalerate, methyl caproate, methyl caprylate, methyl n-octanoate, methyl n-decanoate, ethyl valerate, ethyl caproate, ethyl caprylate, ethyl n-octanoate and ethyl decanoate.

Examples of carboxylic acid derivatives are di-C ₁ -C ₂ -alkyl esters of carboxylic acids such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, especially cyclic carbonates such as ethylene carbonate Borate and propylene carbonate. Ethylene carbonate is preferred.

In association therewith, in the modified polyalkyleneimine (B), a total of 75 mol% or less, preferably 5 to 60 mol% in total of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer, Or a carboxylic acid or a derivative of carboxylic acid.

The tertiary nitrogen atom in the polyalkyleneimine (B) generally does not react with a carboxylic acid or a carboxylic acid or a derivative of a carboxylic acid.

In another embodiment of the invention, the modified polyalkyleneimine (B) obtainable from the alkylene imine polymer and in particular the polyethyleneimine (B1) reacted with one or more ethylenically unsaturated C ₃ -C ₁₀ -carboxylic acid Are used as free acids in the formulations according to the invention.

The modified polyalkyleneimine (B) may have a high molecular weight or low molecular weight anion, which is organic or preferably inorganic, as a counter ion. In the context of the present invention, the high molecular weight anions have an average molecular weight of at least 200 g / mol, for example less than 2500 g / mol, and the low molecular weight anions have a molecular weight of less than 200 g / mol, for example from 17 to 150 g / mol Of molecular weight. Examples of low molecular weight organic counter ions are acetate, propionate and benzoate. Examples of low molecular weight inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate, and hydrogencarbonate.

In one embodiment of the invention, the modified polyalkyleneimine (B) has a cationic charge density of 5 meq / g (milligram equivalent / g) or greater, preferably 5 to 22 meq / g, When referring to the polyalkyleneimine (B), the data in g does not consider the counter ion. The cationic charge density can be determined, for example, by titration, for example, titration with polyvinyl sulfate.

The modified polyalkyleneimine (B) may also contain one or more anionic comonomers in copolymerized form, for example (meth) acrylic acid. However, the cationic polymer (B) containing at least one anionic comonomer in copolymerized form has more cationic charge than the anionic charge per molecule.

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

In one embodiment of the present invention, the molecular weight Mw of the modified polyalkyleneimine (B) ranges from 550 to 1.5 x 10 ⁶ g / mol.

In one embodiment of the invention, the formulations according to the invention each contain, based on the solids content of the formulation of interest,

(A) in the range of 1 to 50% by weight, preferably 10 to 25% by weight,

Modified polyalkyleneimine (B) in a total amount of 0.001 to 5% by weight, preferably 0.05 to 2.5% by weight.

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

In a preferred embodiment of the invention, the formulations according to the invention are free of phosphates and polyphosphates, for example without the aid of trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate, the hydrogenphosphate is contained therein. "No" in conjunction with phosphates and polyphosphates means that in the context of the present invention the total phosphate and polyphosphate content is in the range of 10 wt.% To 0.2 wt.% By weight.

The formulations according to the invention are advantageous for use in washing dishes and / or kitchen utensils, for example.

In another embodiment of the invention, the formulations according to the invention do not contain additional constituents which are advantageous for use, for example, in dishes and / or kitchen utensil cleaning, but can be easily formulated with additional constituents, It is also suitable as a starting material.

In one embodiment of the invention, the formulation according to the invention contains sodium citrate (C). In connection therewith, the term sodium citrate comprises monosodium salts and preferably disodium salts. Sodium citrate can be used as an anhydrous salt or hydrate, for example as a dihydrate.

In one embodiment of the invention, the formulations according to the invention comprise:

(D) at least one compound selected from alkali metal percarbonates, alkali metal perborates and alkali metal persulfates, also referred to in the context of the present invention as "bleaching agent (D) ".

Preferred bleaching agents (D) are selected from sodium perborate, anhydrous or monohydrate or tetrahydrophthalate, sodium percarbonate, anhydrous or monohydrate, for example monohydrate, and sodium persulfate, Sulfate "includes peracid H ₂ SO ₅ and also salts of peroxydisulfate.

In that context, the alkali metal salts may in each case also be alkali metal hydrogencarbonates, alkali metal hydrogen perborates and alkali metal hydrogen perphosphates. However, dialkyl metal salts are preferred in each case.

In one embodiment of the invention, the formulation according to the invention comprises in each case from 0 to 50% by weight of sodium citrate (C), determined as anhydrous sodium citrate, based on the solids content of the formulation of interest, (C), in each case in an amount of from 1 to 15% by weight, preferably at least 0.5% by weight, based on the solids content of the object of interest, of an alkali metal percarbonate , An alkali metal perborate, and an alkali metal persulfate (D).

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

In one embodiment of the invention, the formulations according to the invention contain 0.1 to 10% by weight of water, based on the total solids of the formulations of interest.

In one embodiment of the invention, the formulations according to the invention are free of heavy metal compounds, in particular from iron and bismuth compounds, which do not act as bleaching catalysts. In connection with heavy metal compounds, "none" means that the content of heavy metal compounds which do not act as bleaching catalyst in the context of the present invention is determined on the basis of the Leach method and solids content, and is in the range of 0 to 100 ppm total . Preferably, the heavy metal content in the formulation according to the present invention is less than 0.05 ppm based on the solids content of the formulation of interest.

In the context of the present invention, "heavy metal" is any metal having a specific gravity of at least 6 g / cm ³ . In particular, the heavy metals are precious metals and also zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.

Preferably, the formulations according to the invention contain a non-measurable fraction, for example less than 1 ppm zinc and bismuth compounds.

In one embodiment of the invention, the formulation according to the invention comprises a further component (E), for example one or more surfactants, one or more enzymes, one or more builders, in particular non-containing builders, one or more One or more bleach activators, one or more bleach stabilizers, one or more antifoaming agents, one or more corrosion inhibitors, one or more builders, a buffer, a dye, one or more flavoring agents, One or more inorganic solvents, one or more tableting aids, one or more disintegrants, one or more thickeners, or one or more solubility promoters.

Examples of surfactants are, in particular, nonionic surfactants and also mixtures of anionic or zwitterionic surfactants with nonionic surfactants. Preferred nonionic surfactants include alkoxylated alcohols and alkoxylated fatty alcohols, bi- and multi-block copolymers of ethylene oxide and propylene oxide, reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amines It's an oxide.

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

(Where the variables are defined as follows:

R ¹ is the same or different and is selected from linear C ₁ -C ₁₀ -alkyl, preferably ethyl and particularly preferably methyl,

R ² is 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 is selected from the group consisting of C ₁ -C ₁₀ -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.- Pentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl,

m and n are in the range of 0 to 300, and the sum of n and m is 1 or more. Preferably, m ranges from 1 to 100 and n ranges from 0 to 30.

Here, the compound of formula (I) may be a block copolymer or a random copolymer, preferably a block copolymer.

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

(Where the variables are defined as follows:

R ¹ the same or different and are linear C ₁ -C ₄ is -alkyl, preferably equally, ethyl, and particularly preferably in each case is selected from methyl,

R ⁴ is selected from C ₆ -C ₂₀ -alkyl, especially 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 is a number ranging from 1 to 6,

b is a number ranging from 4 to 20,

and d is a number in the range of 4 to 25).

Here, the compound of formula (II) may be a block copolymer or a random copolymer, preferably a block copolymer.

Another suitable nonionic surfactant is selected from the double- and multi-block copolymers composed of ethylene oxide and propylene oxide. Another suitable nonionic surfactant is selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl glycosides are likewise suitable. A summary of another suitable non-ionic surfactant can be found in EP-A 0 851 023 and DE-A 198 19 187.

Mixtures of two or more 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 from 1 to 6 ethylene oxide units per molecule .

In one embodiment of the invention, the formulations according to the invention may comprise surfactants in the range of 3 to 20% by weight.

The formulations according to the invention may comprise one or more enzymes. Examples of enzymes are lipase, hydrolase, amylase, protease, cellulase, esterase, pectinase, lactase and peroxidase.

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

In addition to sodium citrate (C), the formulations according to the invention may contain one or more builders, in particular builders without phosphate. Examples of suitable builders are the silicate, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, in particular 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 Aliphatic sulfonates, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, tartaric acid monoacetate, tartaric acid monoacetate, Oxidized starch, and polymeric builders such as polycarboxylate and polyaspartic acid.

In one embodiment of the invention, the builder is selected from polycarboxylates, for example alkali metal salts of (meth) acrylic acid homopolymers 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. Suitable polymers are, in particular, polyacrylic acids with an average molecular weight M _w preferably in the range from 2000 to 40 000 g / mol, preferably from 2000 to 10 000 g / mol, especially from 3000 to 8000 g / mol. Also suitable are copolymeric polycarboxylates, particularly those of acrylic acid and methacrylic acid, and those of acrylic acid, methacrylic acid and maleic acid and / or fumaric acid.

Also preferred are monoethylenically unsaturated C ₃ -C ₁₀ -mono- or dicarboxylic acids such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, or anhydrides thereof It is also possible to use copolymers of one or more monomers with one or more hydrophilic or hydrophobically modified monomers as shown below.

Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene such as 1-decene, 1-dodecene, 1-tetradecene, 1- hexadecene, Olefins having 10 or more carbon atoms such as 1-eicosene, 1-doococene, 1-tetracosen and 1-hexacosene, or mixtures thereof, C ₂₂ -olefins, C ₂₀ -C _24- Is a mixture of polyisobutene having an average of 12 to 100 carbon atoms.

Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, and also nonionic monomers having hydroxyl functional groups or alkylene oxide groups. (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypoly (propyleneoxy) acrylate, methoxypolyethylene glycol (meth) (Meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate and ethoxypoly (Propylene oxide-co-ethylene oxide) (meth) acrylate. Wherein the polyalkylene glycol comprises from 3 to 50, in particular from 5 to 40 and in particular from 10 to 30, alkylene oxide units.

Particularly preferred monomers containing sulfonic acid groups here are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2- acrylamido-2-methylpropanesulfonic acid, 2- 2-hydroxy-3- (2-hydroxypropyl) -sulfonic acid, 2-hydroxypropylsulfonic acid, methallylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, 2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfo Methacrylamides, sulfomethylmethacrylamides, and the salts of these acids, such as the sodium, potassium or ammonium salts thereof.

Particularly preferred monomers containing phosphonate groups are vinyl phosphonic acids and their salts.

Amphoteric polymers can also be used as builders.

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

In one embodiment of the invention, the formulations according to the invention may comprise one or more co-builders.

Examples of nose builders are phosphonates, such as hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a co-builder. It is preferably used as the sodium salt, the disodium salt is neutral and the tetrasodium salt is alkaline (pH 9). Suitable aminoalkane phosphonates are preferably ethylene diamine tetramethylene phosphonate (EDTMP), diethylenetriaminepenta methylene phosphonate (DTPMP), and also their higher homologs. They are preferably used in the form of a neutrally reacting sodium salt, for example as a hexasodium salt of EDTMP or as a hepta- and octasodium salt of DTPMP.

Formulations according to the present invention may comprise one or more alkali carriers. The alkali carrier provides a pH of 9 or higher, for example, when an alkaline pH is required. For example, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates are suitable. The preferred alkali metal is in each case potassium, particularly preferred is sodium.

In addition to the bleaching agent (D), the formulations according to the invention may contain one or more chlorine bleaching agents.

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

The formulations according to the invention may contain, for example, from 3 to 10% by weight of a chlorine bleach.

The formulations according to the invention may comprise one or more bleach catalysts. The bleach catalyst may be a bleach-activating transition metal salt and / or a transition metal salt such as, for example, a manganese-, iron-, cobalt-, ruthenium- or molybdenum- salen complex or a manganese-, iron-, cobalt-, ruthenium- or molybdenum- Transition metal complexes. It is also possible to use manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing triangular ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes as bleach catalysts Do.

Formulations in accordance with the present invention may include one or more bleach activators such as N-methylmorpholinium-acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts such as N -Acylimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT") or nitrile quats (trimethylammonium acetonitrile salt) .

Other examples of suitable bleach activators are tetraacetyl ethylenediamine (TAED) and tetraacetyl hexylenediamine.

The formulations according to the invention may comprise one or more corrosion inhibitors. In the case of the present invention, this should be understood to mean a compound which inhibits corrosion of the metal. Examples of suitable corrosion inhibitors include, but are not limited to, triazoles, especially benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, and also, for example, hydroquinone, pyrocatechin, hydroxyhydroquinone, ≪ / RTI >

In one embodiment of the invention, the formulation according to the invention comprises a total of 0.1 to 1.5% by weight corrosion inhibitor.

The formulations according to the invention may comprise one or more builders, for example sodium sulphate.

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

In one embodiment of the invention, the formulation according to the invention contains from 0.05 to 0.5% by weight of total defoamer.

The formulations according to the invention may contain phosphoric acid or one or more phosphoric acid derivatives, for example hydroxyethan-1,1-diphosphonic acid.

The invention also provides the use of the formulations according to the invention for the mechanical washing of ceramics and utensils. In the context of the present invention, the utensils mentioned are, for example, pots, fans, casseroles, and also metallic objects such as skimmers, fish slices and garlic daggers.

It is preferred that the formulations according to the invention are used for machine washing of objects with at least one surface being glass, which may or may not be decorated. In this regard, in the context of the present invention, it is to be understood that the glass surface means that the object has one or more glass portions that are in contact with the ambient air and can be contaminated during use of the object. Thus, the object may be made essentially of glass, such as a glass cup or a glass bowl. However, they may also be, for example, a lid having individual elements made of another material, for example a port lid having a metallic rim and a handle.

The glass surface can be decorated, e.g. colored or printed, or not decorated.

The term "glass" includes any desired glass, such as lead glass and in particular soda lime glass, crystal glass and borosilicate glass.

Preferably, the machine cleaning is a dishwasher-based cleaning (automatic dishwashing).

In one embodiment of the invention, one or more formulations according to the invention are used for machine washing of glass cups, glass vases and glassware for cooking.

In one embodiment of the present invention, it is understood that water having a hardness in the range of 1 to 30 degrees Deutsche Hardness, preferably in the range of 2 to 25 Deutsche Hardness is used for cleaning, and the Deutsche Hardness is in particular the calcium hardness do.

For rinsing, it is possible to use water having a hardness in the range of 1 to 30 DEG German hardness, preferably in the range of 2 to 25 DEG German hardness.

When the formulation according to the invention is used for mechanical cleaning, even when repeatedly machine washing of objects with at least one surface of glass, only very low glass corrosion tendencies are observed and the object or objects on which one or more of the surfaces are glass- It is cleaned together with ceramics. Also, it is considerably less harmful to use the glass cleansing formulations according to the invention with metal objects, for example with pots, pans or garlic dodge.

Furthermore, it can be observed that the formulation according to the present invention has a very good bleaching effect when used in dishes and kitchen utensils and glass surface cleaning.

The present invention further provides a process for the preparation of the formulation of the invention, which is also abbreviated to the process according to the invention. For carrying out the process according to the invention, the process is carried out, for example, in the presence of water, in one or more stages, by mixing,

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

(B) at least one alkyleneimine polymer covalently modified with at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of a carboxylic acid, wherein the nitrogen of the primary and secondary amino groups of the alkyleneimine polymer Up to 75 mole% of the atoms are reacted with a carboxylic acid or a carboxylic acid or a derivative of a carboxylic acid,

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),

After which it may entail completely or partially removing the water.

The compound (A), the modified polyethyleneimine (B) and the bleaching agent (D) are defined above.

In one embodiment of the present invention, before removing at least some of the water, one or more further components (E) of the formulation according to the invention, for example one or more surfactants, one or more enzymes, one or more builders, One or more builders, one or more builders, one or more builders, one or more builders, one or more builders, one or more builders, one or more builders, one or more builders, one or more builders, one or more builders, It is possible to mix with the dye.

In one embodiment, the procedure is carried out, for example, from a formulation according to the invention, by evaporation, especially by spray-drying, spray-granulating or consolidating, to a residual moisture in the range of 0 to 5% Completely or partially removed.

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

In one embodiment of the invention, water is completely or partially removed at a temperature in the range of from 60 to 220 占 폚.

By the production method according to the present invention, the formulation according to the present invention can be easily obtained.

The cleaning formulations according to the present invention may be presented in the form of single or multi-phase liquids or solids, in tablets or in the form of other quantities, in packaged or unpackaged form. The water content of the liquid formulation may vary from 35 to 90% water.

The present invention will be described with reference to working examples.

General: After weighing and visual evaluation of the glass, the first cleaning of the specimen was carried out in a household dishwasher and the specimen was treated with only clean cotton gloves to prevent the weight and / or visual impression of the specimen from being modulated.

The data in% is by weight unless otherwise stated.

I. Formulation according to the present invention

The charge density of the modified polyethyleneimine (B) is determined as follows (Reference: Horn, Prog. Colloid & Polym. Sci. 1978, 65, 251)

1 g of the (co) polymer of interest (B) is dissolved in 100 ml of demineralized water. Using a buffer solution and aqueous HCl, a pH of 4.0 as determined by the potential difference was established. 3 ml of a toluidine blue aqueous solution (50 mg / l in water) was added, and N / 400-KPVS (potassium polyvinyl sulfate) solution (Wako) having a concentration of 0.0004 meq / ml was titrated until the color changed from blue to pink did. The charge density was calculated as follows:

LA = 0.4 KV

[Wherein,

LA: charge density of the modified polyethyleneimine (B) of interest, expressed in meq / g (milligram equivalents / g)

KV: consumption of N / 400-KPVS solution, ml].

I.1 Preparation of basic mixtures

First, the basic mixture was prepared from the injection material according to Table 1. The injection material was dry blended.

≪ tb > TABLE 1 < tb > ______________________________________ <

Abbreviation:

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

I.2.1 Preparation of formulations 2 to 13 and comparative formulations C1 to C8 according to the invention

Modified polyethyleneimine (B) according to Table 2 was used:

Table 2: Modified polyethyleneimine

The molecular weight Mw was determined in each case on the polyethyleneimine phase, i.e. before the modification. The functionalization refers to the sum of the primary and secondary N atoms in the polyethyleneimine of interest.

process:

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

The mixture was then stirred for 10 minutes. MGDA trisodium salt (A.1), dissolved in 30 ml of water, was added according to Table 3. This provided a clear solution. The base mixture according to Table 3 was then added, the mixture was stirred again, and the water was evaporated.

During the test, when the corresponding fraction of the base mixture is metered separately from the aqueous solution of (A.1), (B), (C.1) or (D.1), the dried formulation with the same amount of active ingredient is tested Lt; / RTI > Therefore, the order of metering addition is not a problem.

Additionally, 2.5% by weight of polyvinyl alcohol during compression will provide a formulation with improved powder shape (particle size, bulk density) and reduced air absorption in the air.

II. Use of formulations according to the invention and comparative formulations for machine washing of glass

General: After the first cleaning of the specimen in the household dishwasher until after the weighing and visual evaluation of the glass, the specimen was handled using only a clean cotton glove so that the weight and / or visual impression of the specimen was not damaged.

Tests of formulations and comparative formulations according to the invention were carried out as follows.

II.1 Method for dishwasher using continuous operation

Dishwasher: Miele G 1222 SCL

Program: 65 ° C (pre-cleaned)

Supplies: 3 "GILDE" champagne glasses, 3 "INTERMEZZO" brandy glasses

For rinsing, the goblets were put in the bowl basket at the top of the dishwasher. The dishwashing agent used in each case was 25 g of the inventive formulation or 25 g of the comparative formulation as shown in Table 2 and Table 2 shows in each case the active ingredient (A.1), the base mixture, the silicate (C.1 or C .2) and the compound (D) or (E) and the formulation (B) according to the present invention. Washing was carried out at a rinse-rinse temperature of 55 ° C. The water hardness was 0 to 2 ° German hardness in each case. Washing was carried out in each case for 100 washing cycles, that is, the program was run 100 times. Evaluation after 100 washing cycles was carried out gravimetrically and visually.

The weight of the glass was determined before the initiation of the first washing cycle and after drying after the last washing cycle. The weight loss is the difference between the two values.

In addition to the gravimetric evaluation, the visual evaluation of the article after 100 cycles in a darkened chamber with light behind a perforated plate was carried out using a 1 (very poor) to 5 (very good) grade scale. In that context, the grades were determined for corrosion / fog and / or line corrosion in each case.

Experimental process:

For the purpose of pretreatment, the specimens were first washed in a household dishwasher (Bosch SGS5602) using 1 g of surfactant (nC ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH) and 20 g of citric acid did. The test specimens were dried, their weights were determined and they were fixed in a mesh base insert.

To evaluate the weighing wear, the dry test piece was weighed. The visual evaluation of the test specimens was then carried out. For this purpose, the surface of the test piece was evaluated for line corrosion (free ridge) and turbid corrosion (sheet opacity).

Evaluation was carried out according to the following form.

Line corrosion:

L5: Line not visible

L4: slight line formation in very small areas, fine line corrosion

L3: Line corrosion in a certain area

L2: Line corrosion in multiple zones

L1: Severe line corrosion

Glass turbidity

L5: No visible turbidity

L4: slight turbidity in very small areas

L3: Turbidity in a certain area

L2: turbidity in several areas

L1: Serious opacity over almost all glass surfaces

Also, during the evaluation, intermediate ratings (e.g., L3-4) were accepted.

II.3 Results

The results are summarized in Table 3.

In embodiments of the present invention, there was only weak or no glass corrosion.

When water of 2 ° German hardness was used in the test instead of water, the formulation according to the invention was also superior to the corresponding comparative formulation in terms of glass corrosion protection.

Table 3: Test results using dishwasher (continuous operation)

Claims (15)

Formulation containing:
(A) at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof, and
(B) at least one alkyleneimine polymer covalently modified with at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of a carboxylic acid, wherein the nitrogen of the primary and secondary amino groups of the alkyleneimine polymer Up to 75 mole% of the atoms react with carboxylic acids or carboxylic acid or derivatives of carboxylic acids. The formulation of claim 1, wherein the formulation is free of phosphate and polyphosphate. The formulation of claim 1 or 2, wherein the covalently modified alkylene imine polymer (B) is selected from alkylene imine polymers as follows:
(B1) is reacted with one or more ethylenically unsaturated C ₃ -C ₁₀ -carboxylic acids, or
(B2) is reacted with at least one C ₅ -C ₁₂ -carboxylic acid free of ethylene double bonds,
(B3) is reacted with at least one carboxylic acid ester,
(B4) reacted with hydroxyanic acid and formaldehyde. 4. A formulation according to any one of claims 1 to 3 having a heavy metal content of less than 0.05 ppm based on the solids content of the formulation of interest. 5. The method according to any one of claims 1 to 4, wherein the alkylene imine polymer (B) contains 5 to 60 mol% of the total nitrogen atoms of the primary and secondary amino groups of the alkylene imine polymer, Lt; RTI ID = 0.0 > acid. ≪ / RTI > 6. A formulation according to any one of claims 1 to 5 which is solid at room temperature. The formulation according to any one of claims 1 to 6, wherein the water content is in the range of 0.1 to 10% by weight. The formulation according to any one of claims 1 to 7, wherein the covalently modified alkylene imine polymer (B) has a cationic charge density of at least 5 meq / g. 9. A formulation according to any one of claims 1 to 8, in each case based on the solids content of the formulation of interest, comprising:
Amino carboxylates (A) in the total amount ranging from 1 to 50% by weight,
Covalently modified alkyleneimine polymer (B) in a total amount of 0.001 to 5% by weight.  Use of a formulation as claimed in any one of claims 1 to 9 for cooking and cleaning utensils, wherein the cleaning is carried out with a water bath having a hardness of 2 to 25 DEG German hardness. Use of a formulation according to any one of claims 1 to 9 for the cleaning of objects with one or more surfaces made of glass, which may or may not be decorated. The use according to claim 10 or 11, wherein the washing is washing with a dishwasher. 13. Formulation according to any one of claims 10 to 12, wherein at least one of the formulations according to any one of claims 1 to 8 is used for cleaning glassware, glass vases and glassware for cooking. (A) aminocarboxylates selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof, and
(B) at least one alkylene imine polymer covalently modified with at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of a carboxylic acid, wherein the ratio of the primary and secondary amino groups of the alkylene imine polymer Up to 75 mole% of the nitrogen atoms are reacted with a carboxylic acid or a carboxylic acid or a derivative of a carboxylic acid,
10. The process according to any one of claims 1 to 9, wherein the additional ingredients are mixed with one another in one or more steps in the presence of water, and then the water is completely or partially removed. 15. The method according to claim 14, wherein the water is removed by spray-drying by spray-drying or spray-granulation.