JP6162791B2 - Formulations, their use as dishwashing compositions or their use to produce dishwashing compositions, and their manufacture - Google Patents

Description

The present invention
(A) at least one aminocarboxylate selected from methylglycine diacetic acid (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetic acid (GLDA), and salts thereof;
(B) at least one alkyleneimine polymer covalently modified with at least one carboxylic acid, or at least one carboxylic acid derivative, or at least one carbonic acid derivative (provided that the primary of the alkyleneimine polymer) And at most 75 mol% of the nitrogen atoms of the secondary amino group are reacted with the carboxylic acid or carboxylic acid derivative or carbonic acid derivative),
Relates to a formulation comprising

  Furthermore, the present invention relates to a process for the preparation of the formulation according to the invention and to the use of the formulation as or for the production of a dishwashing composition, in particular for machine dishwashing.

  Dishwashing compositions must meet a number of requirements. Thus, they must radically clean the dishes, they should not contain harmful or potentially harmful substances in the wastewater, they are desorbed of water from the dishes (Run-off) and drying should be possible, and they should not cause problems during operation of the dishwasher. Finally, they should not cause aesthetically undesirable results to the product to be cleaned. In this context, in particular, glass corrosion should be mentioned.

  Glass corrosion is mainly caused by chemical action, not only as a result of mechanical action, for example, glass rubbing against each other, or mechanical contact between the glass and the dishwasher parts. For example, certain ions may elute from the glass through repeated mechanical cleaning, but this changes to worsen the optical and thus aesthetic properties.

  Several effects are observed in the event of glass corrosion. First, the generation of microscopically fine cracks can be observed, which becomes apparent in the form of lines. Second, in many cases, overall haze, such as roughening, can be observed, which makes the glass look unattractive. This type of effect is also generally subdivided into iridescent discoloration, ridge formation, and sheet and annular haze.

  It is known from WO 2002/64719 that certain copolymers of ethylenically unsaturated carboxylic acids and, for example, esters of ethylenically unsaturated carboxylic acids can be used in dishwashing compositions.

  WO 2006/108857 discloses alkoxylated polyethyleneimine as an additive to detergents. By way of example, a detergent is disclosed which comprises a zeolite or a polyaminocarboxylate such as EDTA or triethylenediaminepentaacetic acid as complexing agent.

  WO 01/96516 proposes a formulation comprising an alkoxylated polyethyleneimine for cleaning hard surfaces. Purified water is used for rinsing.

  WO 2010/020765 discloses a dishwashing composition comprising polyethyleneimine. This type of dishwashing composition may or may not contain phosphate. They are said to have good prevention of glass corrosion. Zinc- and bismuth-containing dishwashing compositions are not recommended. In many cases, however, glass corrosion, in particular linear corrosion and haze, is not properly prevented or prevented from proceeding.

WO 2002/64719 WO 2006/108857 WO 01/96516 WO 2010/020765 EP-A 0 851 023 DE-A 198 19 187

Horn, Prog. Colloid & Polym. Sci. 1978, 65, 251

  Thus providing a formulation which is suitable as a dishwashing composition or for producing a dishwashing composition and which avoids the disadvantages known from the prior art, prevents the corrosion of the glass or at least reduces it particularly well The purpose was to do. Furthermore, it was also an object to provide a method for producing a formulation which is suitable as a dishwashing composition or for producing a dishwashing composition and which avoids the disadvantages known from the prior art. It was also an object to provide a method of using the formulation.

  Correspondingly, the initially specified formulation (also abbreviated as the formulation according to the invention) was found.

The formulation according to the invention is
(A) at least one aminocarboxylate selected from methylglycine diacetic acid (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetic acid (GLDA), and salts thereof (within the context of the present invention, Also, aminocarboxylate (A), otherwise abbreviated as compound (A)),
including.

Compound (A) is preferably selected as the free acid, particularly preferably in a partially or fully neutralized form, ie as a salt. Suitable counterions are, for example, inorganic cations such as ammonium, alkali metals or alkaline earth metals, preferably Mg ²⁺ , Ca ²⁺ , Na ⁺ , K ⁺ , or organic cations, preferably one or more Ammonium substituted by organic groups, especially triethanolammonium, N, N-diethanolammonium, N-mono-C ₁ -C ₄ -alkyldiethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium And N, N-di-C ₁ -C ₄ -alkylethanolammonium.

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

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

Furthermore, the formulation according to the invention is
(B) at least one alkyleneimine polymer covalently modified with at least one carboxylic acid, or at least one carboxylic acid derivative, or at least one carbonic acid derivative (also short, modified polyalkyleneimine ( B)), wherein at least 75 mol% of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer have reacted with the carboxylic acid or carboxylic acid derivative or carbonic acid derivative. ,
including.

  Within the context of the present invention, an alkyleneimine polymer is a polymeric material obtained by homo- or copolymerization of one or more cyclic imines or by grafting at least one cyclic imine to a (co) polymer. Should be understood to mean. Examples are polyalkylene polyamines and polyimide amines grafted with ethyleneimine.

Within the context of the present invention, the polyalkylene polyamine preferably comprises at least 6 nitrogen atoms and at least 5 C ₂ -C ₁₀ -alkylene units, preferably C ₂ -C ₃ -alkylene units per molecule. It is understood to mean a polymer comprising, for example pentaethylenehexamine, in particular polyethyleneimine.

The polyalkylene polyamine, in particular polyethyleneimine, may for example have an average molecular weight (M _w ) of at least 300 g / mol; preferably the average molecular weight of the alkyleneimine polymer is determined by gel permeation chromatography (GPC) It 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, in particular C ₁ -C ₁₀ -alkyl chlorides, such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide. N-butyl chloride, tert-butyl chloride, n-hexyl chloride, as well as epichlorohydrin, dimethyl sulfate, diethyl sulfate and benzyl chloride. As an alkyleneimine polymer, when a polyalkylene polyamine that is quaternized (alkylated) is covalently modified, the degree of quaternization (alkylation) can be quaternized in the alkyleneimine polymer. Preferably from 1 to 25, particularly preferably up to 20 mol%, relative to the N atom (which can be alkylated).

Furthermore, polyalkylene polyamines, especially polyethyleneimines, as alkylene imine polymer, C 2 _-C 22 _- partially alkoxylated form epoxide may be covalently modified. Suitable _C 2 _{-C 22} - Examples of epoxides include ethylene oxide, propylene oxide, n- hexylene oxide, styrene oxide. As alkylene imine polymer, C 2 _-C 22 _- polyalkylene polyamines which partially alkoxylated with epoxide, when modified by the covalent bond, the degree of alkoxylation, alkoxylated possible N atoms in the alkylene imine polymer On the other hand, it is preferably 1 to 25, particularly preferably 20 mol%.

Furthermore, polyamidoamines grafted with ethyleneimine are suitable as alkyleneimine polymers. Suitable polyamidoamines can be obtained, for example, by reacting C ₄ -C ₁₀ -dicarboxylic acids with polyalkylene polyamines preferably containing 3 to 10 basic nitrogen atoms in the molecule. Suitable dicarboxylic acids such as succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is also possible to use a mixture of said dicarboxylic acids, for example a mixture of adipic acid and glutaric acid or a mixture of maleic acid and adipic acid. In order to produce polyamidoamine, it is preferable to use adipic acid. Suitable polyalkylene polyamines condensed with the dicarboxylic acid are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, and bis-aminopropylethylenediamine. Said polyalkylene polyamines may also be used in the form of mixtures in the production of polyamidoamines. The production of the polyamidoamine is preferably carried out without dilution, but may optionally be carried out in an inert solvent. The condensation of the dicarboxylic acid and the polyalkylene polyamine occurs at an elevated temperature, for example, in the range of 120 to 220 ° C. Water produced during the reaction is distilled off from the reaction mixture. The condensation may optionally be carried out in the presence of a lactone or lactam of a carboxylic acid having 4 to 8 carbon atoms. Usually 0.8 to 1.4 mol of polyalkylene polyamine is used per mol of dicarboxylic acid. The polyamidoamine thus obtained has primary and secondary NH groups and is soluble in water.

  The polyamidoamine grafted with ethyleneimine is such that ethyleneimine acts on the polyamidoamine in the presence of brainsted acid or Lewis acid, for example sulfuric acid, phosphoric acid or boron trifluoride etherate. Can be manufactured. As a result, ethyleneimine is grafted onto the polyamidoamine. For example, 1 to 10 ethyleneimine units can be grafted per one basic nitrogen atom of the polyamidoamine, ie 10 to 500 parts by weight of ethyleneimine is used per 100 parts by weight of polyamidoamine. .

  A preferred alkyleneimine polymer is polyethyleneimine.

In one embodiment of the invention, 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, particularly preferably in the range of 800 to 25,000 g / mol. Having an average molecular weight (M _w ), which can be determined, for example, by gel permeation chromatography (GPC).

In one embodiment of the invention, the polyethyleneimine is selected from hyperbranched polyethyleneimine. Hyperbranched polyethyleneimines are characterized by their high degree of branching (DB). The degree of branching can be determined, for example, by ¹³ C-NMR spectroscopy, preferably in D ₂ O, and is defined as follows:
DB = D + T / D + T + L
D (dendritic) corresponds to the ratio of tertiary amino groups, L (linear) corresponds to the ratio of secondary amino groups, and T (terminal) corresponds to the ratio of primary amino groups To do.

  Within the context of the present invention, hyperbranched polyethyleneimines are 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, especially very Preferably, it is a polyethyleneimine having a DB of at least 0.5.

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

  Within the context of the present invention, the alkyleneimine polymer is used in a covalently modified form, in particular a large total of nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer. Even up to 75 mol%, preferably a total of 5 to 60 mol%, is used in a form reacted with at least one carboxylic acid, or at least one carboxylic acid derivative, or at least one carbonic acid derivative. Within the context of the present application, the reaction (modification) can thus be, for example, alkylation or amide.

In one embodiment of the invention, the modified polyalkyleneimine (B) is
(B1) was reacted with at least one ethylenically unsaturated _C 3 _{-C 10} carboxylic acid, or (B2) at least one no ethylenic double bond _C 5 _{-C 12} - reacted with a carboxylic acid ,
(B3) reacted with at least one carbonate, and (B4) reacted with hydrocyanic acid and formaldehyde, for example in the sense of Strecker synthesis,
It is selected from alkyleneimine polymers, in particular polyethyleneimine.

Ethylenically unsaturated _C 3 _{-C 10} - Examples of carboxylic acids, unsaturated fatty acids, preferably alpha, beta-ethylenically unsaturated _C 3 _{-C 10} - carboxylic acids, for example, (E) - or (Z) - Crotonic acid, methacrylic acid, especially acrylic acid. As a result of the reaction with carboxylic _{acids, C 3 ~C 10 - - C} 3 ~C 10 carboxylic acid, in the sense of a Michael addition, preferably added to the nitrogen atom of the NH ₂ group or NH groups from an alkylene imine polymer.

_C 5 _{-C 12} no ethylenic double bond - Examples of carboxylic acids are valeric, caproic acid, caprylic acid, n- octanoic acid, n- decanoic acid, and lauric acid. C ₅ -C 12 no ethylenic double bond _- as a result of reaction with a carboxylic acid, preferably, the amide of the nitrogen atom of the NH ₂ group or NH groups from an alkylene imine polymer is carried out.

_C 5 _{-C 12} no ethylenic double bond - Examples of carboxylic acid derivatives, their esters, for _example, C 1 -C ₄ - alkyl ester, in particular ethyl and methyl ester. Examples are methyl valerate, methyl caproate, methyl caprylate, methyl n-octanoate, methyl n-decanoate, ethyl valerate, ethyl caproate, ethyl caprylate, ethyl n-octanoate, and n-decanoic acid Ethyl.

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

  In this connection, in the modified polyalkyleneimine (B), a total of at most 75 mol%, preferably a total of 5 to 60 mol% of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer. Reacts with a carboxylic acid, or a carboxylic acid derivative or a carbonic acid derivative.

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

In another embodiment of the present invention, at least one ethylenically unsaturated C ₃ -C 10 _- alkylene imine polymer reacted with carboxylic acids, particularly modified polyalkyleneimine obtained from polyethylenimine (B1) (B) is Used as the free acid in the formulations of the present invention.

  The modified polyalkyleneimine (B) may have an organic or preferably inorganic high molecular weight or low molecular weight anion as a counter ion. Within the context of the present invention, the high molecular weight anion has an average molecular weight of 200 g / mol or more, for example up to 2500 g / mol, and the low molecular weight anion has a molecular weight of less than 200 g / mol, for example 17 to 150 g / mol. Have. Examples of low molecular weight organic counter ions are acetate ion, propionate ion and benzoate ion. Examples of low molecular weight inorganic counter ions are sulfate ions, chloride ions, bromide ions, hydroxide ions, carbonate ions, methanesulfonate ions and bicarbonate ions.

  In one embodiment of the invention, the modified polyalkyleneimine (B) has a cationic charge density of at least 5 meq / g (millieq / g), preferably 5 to 22 meq / g, the data in g being The present invention relates to a modified polyalkyleneimine (B) that does not include a counter ion. The cationic charge density can be measured, for example, by titration, for example by titration with polyvinyl sulfate.

  The modified polyalkyleneimine (B) can also include one or more anionic comonomers in a copolymerized state, such as (meth) acrylic acid. However, the cationic polymer (B), which also contains one or more anionic comonomers in the copolymerized state, has more cations c per molecule than the anionic charge.

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

In one embodiment of the invention, the modified polyalkyleneimine (B) has a molecular weight (M _w ) in the range of 550 to 1.5 · 10 ⁶ g / mol.

  In one embodiment of the invention, the formulation according to the invention in each case has a total aminocarboxy in the range of 1 to 50% by weight, preferably 10 to 25% by weight, based in each case on the solids content of the formulation. The rate (A), in total, contains the modified polyalkyleneimine (B) in the range 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 comprises compound (A) and modified polyalkyleneimine (B) in a mass ratio of 1000: 1 to 25: 1.

  In a preferred embodiment of the invention, the formulation according to the invention is free of phosphates and polyphosphates (hydrogen phosphate salts are included in these), for example trisodium phosphate, pentasodium tripolyphosphate And hexasodium metaphosphate is not included. “Excluded” with respect to phosphate and polyphosphate is within the scope relevant to the present invention, and the total content of phosphate and polyphosphate is 10 ppm to 0.2 mass%, as determined by mass measurement. Should be understood to mean in the range of

  The formulations according to the invention may contain further ingredients that are advantageous when used, for example, when washing dishes and / or kitchenware.

  In another embodiment of the present invention, the formulation according to the present invention does not contain any additional ingredients that are advantageous, for example when used when washing dishes and / or kitchenware, but can be easily formulated with further ingredients, Therefore, it is suitable as a starting material.

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

In one embodiment of the invention, the formulation according to the invention comprises
(D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate (within the context of the present invention and also referred to as “bleaching agent (D)”) ),
including.

Preferred bleaches (D) are sodium perborate (anhydrous or, for example, as a monohydrate, or as a tetrahydrate or so-called dihydrate), sodium percarbonate (anhydrous, or, for example, The term “persulfate” in each case includes salts of peracid (H ₂ SO ₅ ) as well as peroxodisulfate.

  In this context, the alkali metal salt may in each case also be an alkali metal hydrogen carbonate, an alkali metal perborate, and an alkali metal persulfate. However, in each case a dialkyl metal salt is preferred.

  In one embodiment of the invention, the formulation according to the invention is in each case 0 to 50% by weight of sodium citrate (C), determined as anhydrous sodium citrate, relative to the solids content of the formulation. , Preferably 1 to 30% by weight, particularly preferably at least 5% by weight, selected from sodium citrate (C), alkali metal percarbonate, alkali metal perborate and alkali metal persulfate in total 0 To 15% by weight of bleach (D), preferably at least 0.5% by weight of bleach (D).

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

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

  In one embodiment of the invention, the formulation according to the invention does not contain heavy metal compounds that do not act as bleach catalysts, in particular iron and bismuth compounds. “Not contained” in relation to the heavy metal compound means that the content of the heavy metal compound that does not act as a bleaching catalyst is determined in accordance with the elution (Leach) method within the range relevant to the present invention, and the total content is from 0 to the solid content. It should be understood to mean in the range of 100 ppm. Preferably, the formulation according to the invention has a heavy metal content of less than 0.05 ppm relative to the solids content of the formulation.

Within the context of the present invention, “heavy metal” is any metal having an intrinsic density of at least 6 g / cm ³ . In particular, heavy metals are noble metals, as well as zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.

  Preferably, the formulations according to the invention are free of measurable proportions of zinc and bismuth compounds, i.e., for example less than 1 ppm.

  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 phosphorus. No builder, one or more cobuilders, one or more alkali metal carriers, one or more bleaches, one or more bleach catalysts, one or more bleach activators, one or more Bleach stabilizer, one or more antifoaming agents, one or more corrosion inhibitors, one or more builders, buffering agents, dyes, one or more fragrances, one or more organic solvents, One or more tableting aids, one or more disintegrants, one or more thickeners, or one or more dissolution enhancers may be included.

  Examples of surfactants are in particular nonionic surfactants, as well as mixtures of anionic or amphoteric 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. is there.

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

In the formula, variables are defined as follows:
R ¹ is the same or different and is selected from linear C ₁ -C ₁₀ -alkyl, preferably in each case the same, ethyl, particularly preferably methyl;
R ² is C ₈ -C ₂₂ -alkyl, for example, n-C ₈ H ₁₇ , n-C ₁₀ H ₂₁ , n-C ₁₂ H ₂₅ , n-C ₁₄ H ₂₉ , n-C ₁₆ H ₃₃ , or selected from n-C ₁₈ H ₃₇ ,
R ³ is C ₁ -C ₁₀ -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. -Butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, selected from n-nonyl, n-decyl or isodecyl;
m and n are in the range of 0 to 300, where the sum of n and m is at least 1. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

  Here, the compound of general 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 general formula (II).

In the formula, variables are defined as follows:
R ¹ is the same or different and is selected from linear C ₁ -C ₁₀ -alkyl, preferably in each case the same, ethyl, particularly preferably methyl;
R ⁴ is C ₆ -C ₂₀ -alkyl, in particular n-C ₈ H ₁₇ , n-C ₁₀ H ₂₁ , n-C ₁₂ H ₂₅ , n-C ₁₄ H ₂₉ , n-C ₁₆ H ₃₃ , or selected from n-C ₁₈ H ₃₇ ,
a is a number ranging from 1 to 6;
b is a number in the range of 4 to 20,
d is a number in the range of 4 to 25.

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

  Suitable further nonionic surfactants are selected from di- and multiblock copolymers consisting of ethylene oxide and propylene oxide. Suitable further nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl glycosides are equally suitable. A comprehensive list of suitable further nonionic surfactants can be found in EP-A 0 851 023 and DE-A 198 19 187.

  A mixture 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 1 to 6 ethylene oxide units per molecule. is there.

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

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

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

In addition to sodium citrate (C), the formulation according to the invention may comprise one or more builders, in particular phosphate-free builders. Examples of suitable builders are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, layered silicates, in particular α-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ , δ wherein ones of -Na ₂ Si ₂ O _5, further, fatty sulfonates, alpha-hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinate, tartrate diacetates, tartaric monoacetate, oxidized starch, and Polymer builders such as polycarboxylates and polyaspartic acid.

  In one embodiment of the invention, the builder is selected from polycarboxylates, such as 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 acid, which preferably has an average molecular weight in the range of 2000 to 40,000 g / mol, preferably 2000 to 10,000 g / mol, in particular 3000 to 8000 g / mol (M _w ). Also suitable are polycarboxylates of copolymers, in particular those of acrylic acid and methacrylic acid, and those of acrylic acid or methacrylic acid and maleic acid and / or fumaric acid.

Monoethylenically unsaturated _C 3 _{-C 10} - mono - or _C 4 _{-C 10} - dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic It is also possible to use copolymers of at least one monomer from the group consisting of acids and at least one monomer modified hydrophilicly or hydrophobically listed below.

Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, such as 1-decene, 1-dodecene, 1-tetradecene, 1 A mixture of hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracocene and 1-hexacocene, C ₂₂ -α-olefin, C ₂₀ -C ₂₄ -α-olefin, and on average from 12 per molecule Polyisobutene having 100 carbon atoms.

  Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxyl functional groups or alkylene oxide groups. Examples include 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 Mention may be made of (meth) acrylates, ethoxypolypropylene glycol (meth) acrylates, ethoxypolybutylene glycol (meth) acrylates, and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylates. The polyalkylene glycols here can contain from 3 to 50, in particular from 5 to 40, in particular from 10 to 30, alkylene oxide units per molecule.

  Particularly preferred monomers containing sulfonic acid groups here are 1-acrylamide-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid, 2-methacrylamide- 2-methylpropanesulfonic acid, 3-methacrylamide-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, sulfomethacrylic acid De, sulfomethyl methacrylamide and salts of said acids, such as their sodium, potassium or ammonium salt.

  Particularly preferred monomers containing phosphonate groups are vinyl phosphonic acid and its salts.

  Furthermore, amphoteric polymers can also be used as builders.

  The formulation according to the invention may comprise, for example, a total of 10 to 50% by weight, preferably up to 20% by weight of builder.

  In one embodiment of the invention, the formulation according to the invention may comprise one or more cobuilders.

  Examples of cobuilders are phosphonates such as hydroxyalkane phosphonates and aminoalkane phosphonates. Of the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a cobuilder. It is preferably used as the sodium salt, the disodium salt is neutral and the trisodium salt is alkaline (pH 9). Suitable aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP), and higher homologues thereof. They are preferably used in the form of neutralized sodium salts, for example as the hexasodium salt of EDTMP or as the 7- and 8-sodium salts of DTPMP.

  The formulation according to the invention may comprise one or more alkali carriers. The alkaline carrier provides a pH of at least 9, for example, where an alkaline pH is desired. For example, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides and alkali metal metasilicates are suitable. In each case, the preferred alkali metal is potassium and particularly preferred is sodium.

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

  Suitable chlorine-containing bleaches are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, hypochlorous acid. Magnesium chlorate, potassium hypochlorite, potassium dichloroisocyanurate, and sodium dichloroisocyanurate.

  Formulations according to the present invention may comprise, for example, a chlorine-containing bleach in the range of 3 to 10% by weight.

  The formulation according to the invention may comprise one or more bleach catalysts. The bleach catalyst can be selected from bleach-promoting transition metal salts and / or transition metal complexes such as manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or -carbonyl complexes. As bleaching catalysts, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripodal ligands, as well as cobalt-, iron-, copper- and ruthenium-amine complexes. It is also possible to use it.

  Formulations according to the present invention include one or more bleach activators such as N-methylmorpholinium-acetonitrile salt (“MMA salt”), trimethylammonium acetonitrile salt, N-acylimide, such as N-nonanoyl. Succinimide, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine (“DADHT”) or nitrile quat (trimethylammonium acetonitrile salt) may be included.

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

  Formulations according to the present invention may include one or more corrosion inhibitors. In the case of the present invention, this is to be understood as meaning a compound which prevents the corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, as well as phenol derivatives such as hydroquinone, pyrocatechin, hydroxyhydroquinone, gallic acid, phloroglucin or pyrogallol. is there.

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

  Formulations according to the present invention may contain one or more builders, such as sodium sulfate.

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

  In one embodiment of the invention, the formulation according to the invention comprises in total a defoamer in the range of 0.05 to 0.5% by weight.

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

  The invention further provides a method of using the formulation according to the invention for machine washing of tableware and kitchenware. Within the context of the present invention, the kitchen utensils mentioned are, for example, pans, pans, casserole, as well as metal objects, such as skimmers, fish slices and garlic presses. It is.

  For the mechanical cleaning of objects having at least one surface made of glass (which may or may not be decorated), the method of using the formulation according to the invention is preferred. In this regard, within the context of the present invention, the surface of the glass has at least one part of glass that contacts the surrounding air and can be soiled by using the object. Should be understood to mean. Thus, the object may consist essentially of glass, such as a drinking glass or a glass bowl. However, they can also be, for example, lids with independent components made of another material, for example pot lids with metal ends and handles.

  The glass surface may be decorated, for example, colored or imprinted, or undecorated.

  The term “glass” includes any desired glass, for example lead glass, in particular soda lime glass, crystal glass and borosilicate glass.

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

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

  In one embodiment of the invention, water having a hardness in the range of 1 to 30 ° German hardness, preferably 2 to 25 ° German hardness is used for the cleaning, where the German hardness is in particular the calcium hardness. It should be understood to mean.

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

  When the formulation according to the invention is used for mechanical cleaning, only a very low tendency to corrosion of the glass is observed even if the object with at least one surface made of glass is repeatedly cleaned with a machine. Moreover, this is only the case when objects having at least one surface made of glass have been cleaned together with heavily soiled eating utensils or earthenware. Furthermore, the use of the composition according to the invention for cleaning glass together with objects made of metal, for example together with pans, pans or garlic presses, is significantly less harmful.

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

The present invention further provides a process (also abbreviated as a process according to the invention) for the preparation of a formulation according to the invention. In order to carry out the production method according to the invention, the procedure is, for example,
(A) an aminocarboxylate selected from methylglycine diacetic acid (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetic acid (GLDA), and salts thereof;
(B) at least one alkyleneimine polymer covalently modified with at least one carboxylic acid, or at least one carboxylic acid derivative, or at least one carbonic acid derivative, wherein the first of the alkyleneimine polymer The alkyleneimine polymer, wherein up to 75 mol% of the nitrogen atoms of the primary and secondary amino groups have reacted with the carboxylic acid or carboxylic acid derivative or carbonic acid derivative;
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 component (E) is mixed with one another, eg in one or more steps, eg in the presence of water, eg stirred, and then the water is completely or at least Partial removal may be included.

  Compound (A), modified polyalkyleneimine (B) and bleach (D) are defined above.

  In one embodiment of the invention, before the water is at least partially removed, one or more additional components (E) for the formulation according to the invention and, for example, one or more surfactants Agent, one or more enzymes, one or more builders, one or more cobuilders, in particular a phosphorus-free builder, one or more alkaline carriers, one or more bleaches, one or more A plurality of bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more antifoaming agents, one or more corrosion inhibitors, one or more builders, It can be mixed with a buffer or dye.

  In one embodiment, the procedure consists of completely evaporating water from the formulation according to the invention, in particular by spray drying, spray granulation or compression, or for example from 0.1 to 10% by weight. Including partially removing until the residual moisture in the range.

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

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

  The preparation according to the invention can be easily obtained by the production method according to the invention.

  The cleaning composition according to the invention is provided in liquid or solid form, in one or multiple phases, as a tablet or in the form of other metered units, in packaged or unpackaged form. obtain. The water content of the liquid formulation can vary from 35 to 90% water.

  The invention is illustrated by examples.

  General: After the initial cleaning of the specimen in a home dishwasher, until the glass is weighed and after visual evaluation, the specimen should not be mistaken for mass and / or visual impression. Protected to handle only with clean cotton gloves.

  The data by% is mass% unless otherwise specified.

I. Formulation according to the invention The charge density of the modified polyethyleneimine (B) was always determined as follows (also see Horn, Prog. Colloid & Polym. Sci. 1978, 65, 251).

  1 g of the (co) polymer (B) was dissolved in 100 ml of demineralized water. Using a buffer solution and an aqueous HCl solution, the pH was determined to be 4.0 using a potentiometric method. Add 3 ml of toluidine blue aqueous solution (50 mg / 1 L of water) and titrate with N / 400-KPVS (potassium polyvinyl sulfate) solution (Wako) having a concentration of 0.0004 meq / ml until the color changes from blue to pink. did. The charge density was calculated as follows.

LA = 0.4 ・ KV
here,
LA: charge density of the modified polyethyleneimine (B), meq / g (milli equivalent / g)
KV: Consumption of N / 400-KPVS solution, ml

I. 1 Preparation of base mixture Initially, a base mixture was prepared from raw materials according to Table 1. The raw materials were dry mixed.

Abbreviations MGDA: methyl glycine diacetic acid, trisodium salt TAED: N, N, N ′, N′-tetraacetylethylenediamine HEDP: disodium salt of hydroxyethane (1,1-diphosphonic acid)

I. 2 Production of formulations according to the invention 2.1 This modified polyethyleneimine as indicated from the formulation 2 in the manufacture Table 2 10 and Comparative Formulation C 1 according to the invention (B) was used.

The molecular weight (M _w ) was determined with the original polyethyleneimine, ie in each case before modification. Functionalization indicates the sum of primary and secondary N atoms in the polyethyleneimine.

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

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

  During the test, the corresponding portion of the base mixture can be metered separately from an aqueous solution of (A.1), (B), (C.1) or (D.1) and the same amount The same results were obtained when a dry formulation with the active ingredient was used in the test. Thus, the order of metering is not a problem.

  The addition of 2.5% by weight polyvinyl alcohol during compression results in a formulation with improved powder morphology (granule size, bulk density) and reduced moisture absorption in the air. .

II. Use of formulations according to the invention and comparative formulations for mechanical cleaning of glass General: After initial cleaning of the specimen in a domestic dishwasher, after weighing and visual evaluation of the glass Until now, it was ensured that the specimen was handled only with clean cotton gloves so that the mass and / or visual impression of the specimen was not mistaken.

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

  II. Test method in dishwasher by 1 continuous operation

Dishwasher: Miele G 1222 SCL
Program: 65 ° C (with pre-cleaning)
Product: 3 “GILDE” champagne glasses, 3 “INTERMEZO” brandy glasses

For cleaning, the glasses were arranged in the upper pottery basket of the dishwasher. The dishwashing detergent used is in each case a 25 g formulation according to the invention, as shown in Table 1 and Table 3 , or a 25 g comparative formulation, Tables 1 and 3 being in each case Details of the active ingredient (A.1), base mixture, silicate (C.1 or C.2) and compounds (D) or (E) and (B) of the formulations according to the invention are described. Washing was performed at a clear-rinse temperature of 55 ° C. The hardness of the water was in the range of 0 to 2 ° German hardness in each case. The washing was performed in each case with 100 washing cycles, i.e. the program was run 100 times. The evaluation was performed by mass measurement and visual observation after 100 washing cycles.

  The mass of the glass was determined before the start of the first wash cycle and after drying after the last wash cycle. Mass loss is the difference between these two values.

  In addition to evaluation by mass measurement, after 100 cycles, in the dark room, the light behind the perforated plate was used and the product was rated visually from 1 (very poor) to 5 (very good) This was done using a scale. In this context, in each case, the grade was determined with respect to mottled / fogging and / or linear corrosion.

Experimental Procedure For the purpose of pretreatment, the test specimen was first loaded with 1 g of surfactant (n-C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH) and 20 g of citric acid to remove contaminants. Used and washed in a home dishwasher (Bosch SGS5602). The test bodies were dried, their mass was determined, and they were placed on a mesh base insert.

  In order to evaluate the wear due to mass measurement, the dried specimens were weighed. Subsequently, visual evaluation of the test body was performed. For this purpose, the surfaces of the specimens were evaluated for linear corrosion (glass ridges) and haze corrosion (sheet haze).

  Evaluation was performed according to the following scheme.

Linear corrosion L5: No visible line L4: Slight line formation in very few parts, thin linear corrosion L3: Linear corrosion in few parts L2: Linear corrosion in several parts L1 : Severe linear corrosion Glass fogging
T5 : There is no visible cloudiness
T 4: Slight haze in very few parts
T3 : Cloudiness in a small number of parts
T 2: Cloudiness in some parts
T 1: Severe haze over virtually all glass surfaces During evaluation, intermediate grades (eg L3-4) were also acceptable.

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

  In the examples of the present invention, it was confirmed that there was little glass corrosion or even no glass corrosion.

  In the test, when water was replaced and hard water with 2 ° German hardness was used, the formulation according to the invention was always superior to the corresponding comparative formulation in terms of preventing the corrosion of the glass as well.

Claims (14)

(A) at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA) and salts thereof in a total range of 1 to 50% by weight ,
(B) in the range of 0.001 to 5 mass% in total,
At least one alkyleneimine polymer covalently modified with at least one carboxylic acid or at least one carboxylic acid derivative, or at least one carbonic acid derivative, provided that the primary and secondary alkyleneimine polymers At least 75 mol% of the nitrogen atoms of the amino group are reacted with a carboxylic acid or a carboxylic acid derivative or a carbonic acid derivative) , or at least one alkyleneimine polymer covalently modified with hydrocyanic acid and formaldehyde, Formulation containing.   The formulation of claim 1, which is free of phosphate and polyphosphate. The alkyleneimine polymer (B) modified with a covalent bond is
(B1) at least one ethylenically unsaturated _C 3 to _{-C 10} - reacted alkylene imine polymer and a carboxylic acid, or (B2) at least one no ethylenic double bond _C 5 _{-C 12} - carboxylic An alkyleneimine polymer reacted with an acid,
(B3) an alkyleneimine polymer reacted with at least one carbonate, and (B4) an alkyleneimine polymer reacted with hydrocyanic acid and formaldehyde,
3. Formulation according to claim 1 or 2 selected from.   4. Formulation according to any one of claims 1 to 3, having a heavy metal content of less than 0.05 ppm relative to the solids content of the formulation.   The alkyleneimine polymer (B) is selected from a total of 5 to 60 mol% of nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer reacted with a carboxylic acid or a carboxylic acid derivative. Item 5. The formulation according to any one of Items 1 to 4.   6. Formulation according to any one of claims 1 to 5, which is solid at room temperature.   7. Formulation according to any one of claims 1 to 6, comprising water in the range of 0.1 to 10% by weight.   8. Formulation according to any one of claims 1 to 7, wherein the covalently modified alkyleneimine polymer (B) has a cationic charge density of at least 5 meq / g. Use of a formulation according to any one of claims 1 to 8 for washing earthenware and kitchenware, characterized in that the washing is carried out with water having a hardness of 1 to 30 ° German hardness. Use with. Use of a formulation according to any one of claims 1 to 8 for cleaning objects having at least one surface of glass, which can be decorated or undecorated. Use according to claim 9 or 10 , wherein the washing is a washing with a dishwasher. At least one formulation according to any one of claims 1 8, drinking glasses, is used to wash the vase and glass containers for cooking glass, any of claims 9 11 single Use as described in section. (A) an aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts thereof; and (B) at least one carboxylic acid or at least one At least one alkyleneimine polymer covalently modified with at least one carboxylic acid derivative or at least one carbonic acid derivative, provided that at most the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer Up to 75 mol% is reacted with carboxylic acid or carboxylic acid derivative or carbonic acid derivative) , or at least one alkyleneimine polymer covalently modified with hydrocyanic acid and formaldehyde,
As well as optionally further ingredients are mixed together in one or more steps in the presence of water, and then the water is completely or partially removed,
The method for producing a blend according to any one of claims 1 to 9, wherein: 14. A method according to claim 13 , wherein the water is removed by spray drying or spray granulation.