TW201321497A - Formulations, their use as or for producing dishwashing compositions and their preparation - Google Patents

Abstract

Formulations, their use as or for producing dishwashing compositions and their preparation. Formulations comprising (A) at least one compound selected from aminocarboxylates and polyaminocarboxylates, and salts and derivatives thereof, (B) at least one salt of bismuth, and c at least one homopolymer or copolymer of ethyleneimine.

Description

Use of the formulation, its action or for the manufacture of dishwashing detergent and its preparation

The present invention relates to a compound (A) comprising at least one compound selected from the group consisting of aminocarboxylic acids and polyaminocarboxylic acids and salts and derivatives thereof, (B) at least one phosphonium salt, and (C) at least one extensor A homopolymer or copolymer of ethyl imine.

Furthermore, the invention relates to a process for the preparation of the formulations of the invention and to the use thereof as or for the manufacture of dishwashing detergents, in particular dishwashing detergents for machine dishwashing.

Dishwashing must meet many requirements. Therefore, it must be fundamentally cleaned of the dish, which should be free of harmful or potentially harmful substances in the waste water, which should allow the water to flow out of the tray and dry, and which should not cause problems during the operation of the dishwasher. Finally, it should not be aesthetically undesirable after the appliance to be cleaned. In this regard, glass corrosion is especially mentioned.

Glass corrosion is not only caused by mechanical effects (such as friction by glass or glass in mechanical contact with parts of the dishwasher), but is mainly caused by chemical effects. For example, certain ions can be eluted from the glass via repeated machine washing, which alters the optical properties in an unfavorable manner and thereby alters the aesthetic properties.

In the case of glass corrosion, several effects were observed. First, the formation of microscopic fine lines, which are noticeable in the form of lines, can be observed. Secondly, in many cases, general atomization, such as roughening, can be observed, which makes the glass Unattractive. This type of effect is also subdivided into rainbow-colored fading, ridge formation, and film and ring-like atomization.

US 5,981,456 and WO 99/05248 disclose various dishwashing detergents to which zinc or barium salts can be added to prevent rust or corrosion of the tool.

Certain copolymers of ethylenically unsaturated carboxylic acids with, for example, esters of ethylenically unsaturated carboxylic acids can be used in dishwashing detergents known from WO 2002/64719.

WO 2010/020765 discloses dishwashing concentrates comprising polyethylenimine. This type of dishwashing can contain phosphate or no phosphate. It has a good inhibitory property against glass corrosion. It is recommended that people do not use dishwashing detergents containing zinc and strontium.

However, in many cases, glass corrosion, specifically line corrosion and atomization, cannot be sufficiently delayed or prevented.

Accordingly, it is an object to provide formulations which are suitable for use in the manufacture of dishwashing detergents and which avoid the disadvantages known from the prior art and which inhibit or at least substantially reduce the corrosion of the glass. The object is also to provide a process for the preparation of a formulation suitable for use in the manufacture of dishwashing detergents and avoiding the disadvantages known from the prior art. The purpose is also to provide the use of the formulation.

Accordingly, it has been found that the formulations defined at the outset are also abbreviated as formulations of the invention.

The formulation of the invention comprises (A) at least one compound selected from the group consisting of aminocarboxylic acids and polyaminocarboxylic acids (also abbreviated in the context of the invention as aminocarboxylic acids (A) and polyaminocarboxylic acids (A) or Compound (A)) is also a derivative thereof and a preferred salt.

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

In one embodiment of the invention, compound (A) is selected from the group consisting of aminocarboxylic acids and derivatives of polyaminocarboxylic acids, for example selected from methyl or ethyl esters.

In the context of the present invention, aminocarboxylic acid (A) is understood to mean nitrogen triacetic acid and their organic compounds having a tertiary amine group having one or two CH ₂ -COOH groups It can be partially or completely neutralized as described above. In the context of the present invention, polyaminocarboxylic acids (A) are understood to mean organic compounds having at least two tertiary amino groups, each of which independently has one or two CH ₂ independently of one another. -COOH, which may be partially or completely neutralized as described above.

In another embodiment of the present invention, the aminocarboxylic acid (A) is selected from the group consisting of organic compounds having a secondary amine group having one or two CH(COOH)CH ₂ -COOH groups It can be partially or completely neutralized as described above. In another embodiment of the present invention, the polyaminocarboxylic acid (A) is selected from the group consisting of organic compounds having at least two secondary amine groups each having one CH(COOH)CH ₂ - A COOH group, which may be partially or completely neutralized as described above.

Preferred polyaminocarboxylic acids (A) are selected from the group consisting of 1,2-diaminoethanetetraacetic acid, iminodisuccinic acid (IDS), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid. (HEDTA) and its respective salts, particularly alkali metal salts, in particular sodium salts.

Preferred aminocarboxylic acid (A) and polyaminocarboxylic acid (A) are nitrogen triacetic acid and their organic compounds having an amino acid-based structure, the amine group of which has one or two CH _2- COOH group and is a tertiary amine group. In this regard, the amino acid may be selected from the group consisting of an enantiomeric mixture of an L-amino acid, an R-amino acid, and an amino acid, such as a racemate.

In one embodiment of the present invention, the compound (A) is selected from the group consisting of methylglycine diacetic acid (MGDA), nitrogen triacetic acid, and glutamic acid diacetic acid, and derivatives thereof, and preferably salts thereof, specifically Said its sodium salt. Excellent are methylglycine diacetic acid and MGDA trisodium salt.

The formulations of the present invention comprise at least one water soluble cerium salt (B). The onium salt (B) may be selected from water-soluble and water-insoluble barium salts. In the context of the present invention, in this connection, the cerium salt (B) is said to be water-insoluble when it has a solubility in distilled water of 0.1 g/l or less at 25 °C. Therefore, in the context of the present invention, the onium salt (B) having a higher solubility in water is referred to as a water-soluble phosphonium salt.

In one embodiment of the present invention, the onium salt (B) is selected from the group consisting of barium acetate, barium nitrate, barium sulfate, barium triformate ("barium formate"), barium gallate and barium methanesulfonate, preferably It is a gallic acid bismuth and bismuth methanesulfonate.

In another embodiment of the invention, the onium salt (B) is selected from the group consisting of Bi ₂ O ₃ , aqueous Bi ₂ O ₃ , and BiO(OH). Preferred is BiO(OH).

In one embodiment of the invention, the onium salt (B) is selected from the group consisting of average particle diameters (Average weight) cerium oxide in the range of 10 nm to 100 μm.

The cations in the onium salt (B) may be present in a mismatched form, for example, in combination with an ammonia ligand or a water ligand, and in particular in a hydrated form. In order to simplify the formula, in the context of the present invention, if a system water ligand is used, these ligands are usually omitted.

The onium salt (B) can be converted depending on how the pH of the mixture of the invention is adjusted. Thus, for example, ruthenium acetate or BiCl3 can be used for the preparation of the formulations of the invention, but in an aqueous environment at a pH of 8 or 9, this conversion to BiO(CH ₃ COO) or BiOCl, BiO(OH) or Bi ₂ An aqueous solution of O ₃ which may be present in a non-missing or mismatched form.

The onium salt (B) is preferably present in the form of granules in the formulation of the invention which is a solid at room temperature, the average diameter (average number) of the particles determined by, for example, X-ray scattering, for example, 10 From nm to 100 μm, preferably from 100 nm to 5 μm.

The onium salt (B) is present in dissolved form or in solid form or in the form of a sol in a formulation of the invention which is equivalent to a liquid at room temperature.

The formulations of the present invention additionally comprise: (C) at least one copolymer of ethyleneimine or a preferred homopolymer, also collectively abbreviated as a polyethylenimine (C).

In the context of the present invention, a copolymer of ethyl imine is also understood to mean one or more higher carbon number analogs of ethyl iminoamine (aziridine) and exoethylimine (for example, exfoliation) Iminoimide (2-methylaziridine), 1- or 2-extended butylimine (2-ethylaziridine or 2,3-dimethylaziridine), for example based on exoethyl The fraction of amine, one or more of 0.01 mol% to 75 mol% of exoethylenimine a similar product) copolymer. However, preferred are those which comprise only ethylimine and are in the range of from 0.01 to 5 mol% in the form of a polymerized form of an ethylenimine, and in particular a homopolymer of an ethylenimine. Copolymer.

In one embodiment of the invention, the copolymer of the ethylimine (C) is selected from the group consisting of graft copolymers (C) of ethylenimine. A graft copolymer of this type is also referred to as an extended ethylimine graft copolymer (C) in the context of the present invention. The ethylenimine graft copolymer (C) may or may not be crosslinked.

In one embodiment of the invention, the extended ethylenimine graft copolymer (C) is selected from the group consisting of polymers obtainable by grafting a polyamidoamine with an ethylenimine. Preferably, the extended ethylenimine graft copolymer (C) is grafted from 10% by weight to 90% by weight as a graft base of polyamidoamine and 90% by weight to 10% by weight. The grafting of the ethylenimine composition is in each case based on the extended ethylenimine graft copolymer (C).

Polyamidoamines can be obtained, for example, by condensation of the polyalkylene polyamines in pure form, in the form of a mixture with each other or in the form of a mixture with a diamine.

In the context of the present invention, polyalkylene polyamines are understood to mean compounds which comprise at least three basic nitrogen atoms in their molecule, for example diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylamine. Tetraamine, tetraethylenepentamine, pentaethylenehexamine, N-(2-aminoethyl)-1,3-propanediamine and N,N'-bis(3-aminopropyl)ethylenediamine.

Suitable diamines are, for example, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8- Diaminooctane, isophorone diamine, 4,4'-diaminodiphenylmethane, 1,4-bis(3-aminopropyl)piperazine, 4,9-dioxa-10- Dioxane-1,12-diamine, 4,7,10-trioxatridecane- An α,ω-diamine compound of 1,13-diamine and polyalkylene oxide.

In another embodiment of the present invention, the ethylenimine graft copolymer (C) is selected from the group consisting of polyvinylamines as a graft base and ethylenimine or ethylenimine. A polymer prepared by grafting an oligomer (for example, a dimer or a trimer of ethylenimine). Preferably, the extended ethylenimine graft copolymer (C) is from 10% by weight to 90% by weight of the polyethyleneimine as a graft base and 90% by weight to 10% by weight as a graft-coated ethyl group. The imine composition, in each case, is based on an extended ethylenimine graft copolymer (C).

However, as a component of the formulation of the present invention, at least one polyethylenimine (C) in the form of a homopolymer (preferably uncrosslinked) is preferably selected.

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

In one embodiment of the invention, the average molecular weight M _w of the polyethylenimine (C), which can be determined, for example, by gel permeation chromatography (GPC), is from 500 g/mol to 1 000 000 g/ Within the range of mol, preferably in the range of from 600 g/mol to 75 000 g/mol, particularly preferably in the range of from 800 g/mol to 25 000 g/mol.

In one embodiment of the invention, the polyethylenimine (C) is selected from the group consisting of highly branched polyethylenimines. The highly branched polyethylenimine (C) is characterized by its high degree of branching (DB). The degree of branching can be determined, for example, by ¹³ C-NMR spectrum, preferably in D ₂ O, and is defined as follows: DB = D + T / D + T + L wherein D (dendritic) corresponds to tertiary amine group The fraction, L (straight chain) corresponds to the fraction of the secondary amine group and T (terminal) corresponds to the fraction of the primary amine group.

In the context of the present invention, the highly branched polyethylenimine (C) system DB is in the range from 0.1 to 0.95, preferably from 0.25 to 0.90, particularly preferably in the range from 0.30 to 0.80 and very preferably at least 0.5. Ethylimine (C).

In the context of the present invention, dendritic polyethylenimine (C) is a polyethylenimine (C) having a structurally and molecularly homogeneous structure.

In one embodiment of the invention, the polyethylenimine (C) has an average molecular weight M _w in the range of from 600 g/mol to 75 000 g/mol, preferably from 800 g/mol to 25 000 g/mol. A high degree of branching within the range of polyethylenimine (homopolymer).

According to a particular embodiment of the invention, the polyethylenimine (C) is a high degree branch having an average molecular weight M _{n of} from 500 g/mol to 125 000 g/mol, preferably from 750 g/mol to 100 000 g/mol. Polyethylenimine (homopolymer) selected from dendrimers.

In one embodiment of the invention, the formulation of the invention comprises a total of from 1% to 50% by weight of compound (A), preferably from 10% to 25% by weight, in total from 0.05% to 0.4% by weight. The onium salt (B) in the range, preferably from 0.1% by weight to 0.2% by weight, and a total of from 0.05% by weight to 2% by weight of the homopolymer or copolymer (C) of the ethylenimine, preferably 0.1% by weight Up to 0.5% by weight, in each case based on the solids content of the formulation.

Here, the fraction of the onium salt is given in the form of ruthenium and/or osmium ions. Therefore, the calculation can exclude the fraction of counter ions.

In one embodiment of the invention, the formulation of the invention is immobilized at room temperature Body, such as a powder or lozenge. In another embodiment of the invention, the formulations of the invention are liquid at room temperature. In one embodiment of the invention, the formulations of the invention are granules, liquid formulations or gels.

Without wishing to be given a particular theoretical preference, the onium salt (B) in the formulation of the invention may be present in the form of a miscible ethylimine (C) mismatch.

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

In one embodiment of the invention, the formulations of the invention are free of phosphates and polyphosphates, including hydrogen phosphates, such as trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate. With regard to "free" phosphates and polyphosphates, it is to be understood in the context of the present invention to mean that the total content of phosphates and polyphosphates determined by gravimetric analysis is in the range from 10 ppm to 0.2% by weight.

In one embodiment of the invention, the formulations of the present invention are free of heavy metal compounds which do not function as a bleach catalyst, and in particular are free of iron and zinc compounds. With respect to "free" heavy metal compounds, it is understood in the context of the present invention to mean that the heavy metal compounds which do not have a bleaching catalyst function are determined to have a total content of from 0 to 100 ppm, preferably from 1 ppm to 30 ppm, according to the Leach method. Within the scope.

In the context of the present invention, "heavy metal" is a metal having a specific density of at least 6 g/cm ³ but not germanium. Specifically, heavy metal precious metals are also zinc, iron, copper, lead, tin, nickel, cadmium, and chromium.

Preferably, the formulations of the invention comprise a non-measured number of zinc compounds, i.e., less than 1 ppm.

In one embodiment of the invention, the formulations of the invention may have other Part (D), for example one or more surfactants, one or more enzymes, one or more detergents, in particular phosphorus-free detergents, one or more co-flavoring agents, one or more alkali metal carriers One or more bleaching agents, one or more bleaching catalysts, one or more bleach activators, one or more bleach stabilizers, one or more anti-foaming agents, one or more corrosion inhibitors, one or more detergents, Buffering agents, dyes, one or more perfumes, one or more organic solvents, one or more tableting aids, one or more disintegrants, one or more thickeners, or one or more dissolution promoters.

Examples of the surfactant are specifically a nonionic surfactant and a mixture of an anionic or zwitterionic surfactant and a nonionic surfactant. Preferred nonionic surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multi-block copolymers of ethylene oxide and propylene oxide, and sorbitan and ethylene oxide or rings. The reaction product of oxypropane, alkyl glucoside and the so-called amine oxide.

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the formula (I) Wherein the variables are defined as follows: R ^{1 is} selected from a linear C ₁ -C ₁₀ -alkyl group, preferably an ethyl group and a particularly preferred methyl group, and R ^{2 is} selected from a C ₈ -C ₂₂ -alkyl group, such as 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 C ₁ -C ₁₀ -alkyl, methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, isopentyl, second pentyl, neopentyl, 1,2-dimethylpropyl, iso Amyl, n-hexyl, isohexyl, second hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl or isodecyl, m and n are in the range of 0 to 300, wherein 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 the 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) Wherein the variables are defined as follows: R ^{5 is the} same or different and is selected from a linear C ₁ -C ₄ -alkyl group, preferably in each case the same and being ethyl and more preferably methyl, and R ^{4 is} selected from C ₆ -C ₂₀ -alkyl, specifically 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 in the range of 1 to 6 Number, b is the number in the range of 4 to 20, and d is the number in the range of 4 to 25.

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

Other suitable nonionic surfactants are selected from the group consisting of di- and multi-block copolymers including ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from the group consisting of ethoxylated or propoxylated sorbitan esters. Amine oxide or alkyl Glucosides are also suitable. A review of other suitable nonionic surfactants 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 acid-based anionic surfactant C of ₈ -C ₂₀ - alkyl salts, acids C ₈ -C ₂₀ - alkyl, and salts of C ₈ -C ₂₀ - alkyl ether sulfates, having per molecule 1 to 6 Ethylene oxide unit.

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

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

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

The formulations of the present invention may comprise one or more detergents, in particular phosphate-free detergents. Examples of suitable detergents are phthalates, in particular sodium dicitrate and sodium metasilicate, zeolites, flaky citrates (specifically, they have the formula a-Na ₂ Si ₂ O ₅ , β- Na ₂ Si ₂ O ₅ and δ-Na ₂ Si ₂ O ₅ ), and citric acid and alkali metal salts thereof, succinic acid and alkali metal salts thereof, fatty acid sulfonates, α-hydroxypropionic acid, alkali metal propylene Acid salts, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetates, tartaric acid monoacetates, oxidized starches, and polymeric detergents (eg, polycarboxylates and polyaspartic acid).

In one embodiment of the invention, the detergent is selected from the group consisting of polycarboxylates, for example An alkali metal salt of a (meth)acrylic acid homopolymer or a (meth)acrylic acid copolymer.

Suitable mono-systemic monounsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid are suitable. Suitable polymers are, in particular, polyacrylic acids having an average molecular weight M _{w of} preferably from 2000 g/mol to 40 000 g/mol, preferably from 2000 g/mol to 10 000 g/mol, in particular from 3000 g/mol to In the range of 8000 g/mol. Copolymeric polycarboxylic acids are also suitable, in particular acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid and/or fumaric acid to copolymerize polycarboxylic acids.

It is also possible to use at least one from a monoethylenically unsaturated C ₃ -C ₁₀ -mono- or C ₄ -C ₁₀ -dicarboxylic acid or an anhydride thereof (for example, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, rich A copolymer of a monomer consisting of horse acid, itaconic acid, and citraconic acid with at least one hydrophilic or hydrophobic modified monomer as exemplified below.

Suitable hydrophobic single systems (for example) isobutylene, diisobutylene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, such as 1-decene, 1-12 Alkene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-icosadiene, 1-tetracosene and 1-dihexene, C ₂₂ - A mixture of an α-olefin, a C ₂₀ -C ₂₄ -α-olefin and a polyisobutylene having an average of from 12 to 100 carbon atoms per molecule.

Suitable monomers having a sulfonate or phosphonate group in a hydrophilic single system, and nonionic monomers having a hydroxyl functional group or an alkylene oxide group. For example, mention may be made of allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxy polybutane Alcohol (meth) acrylate, methoxy poly(propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, ethoxy Polypropylene glycol (meth) acrylate, ethoxylated polybutylene glycol (meth) acrylate, and ethoxylated poly(propylene oxide-co-ethylene oxide) (meth) acrylate. Here, the polyalkylene glycol per molecule may comprise from 3 to 50, in particular from 5 to 40 and especially from 10 to 30 alkylene oxide units.

A particularly simple system containing a sulfonic acid group, 1-propenylguanidino-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-propenylamino-2-methyl Propanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 3-methylpropenylamino-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid , allyloxybenzenesulfonic acid, methyl allyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1- Sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethyl decylamine, sulfonate A methacrylamide, and a salt of such an acid (for example, a sodium salt, a potassium salt or an ammonium salt thereof).

A particularly preferred single system vinylphosphonic acid containing a phosphonate group and salts thereof.

In addition, an amphoteric polymer can also be used as a detergent.

The formulations of the present invention may comprise, for example, a total of from 10% to 50% by weight, preferably up to 20% by weight, of a detergent.

The formulations of the present invention may comprise one or more co-flavoring agents.

Examples of co-builders are phosphonates such as hydroxyalkanephosphonates and alkane alkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a co-flavoring agent. It is preferably used in the form of its sodium salt, the disodium salt is neutral and the tetrasodium salt is basic (pH 9). Suitable amino alkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriamine Penta methylene phosphonate (DTPMP), and its higher carbon number analogs. It is preferably used in the form of a neutral reaction sodium salt (for example, in the form of the hexa-sodium salt of EDTMP or in the form of the hepta-sodium and octa-sodium salts of DTPMP).

Formulations of the invention may comprise one or more alkaline carriers. If an alkaline pH is desired, the alkaline carrier provides, for example, a pH of at least 9. For example, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal bismuth phthalates are suitable. In each case, the preferred alkali metal is potassium, and more preferably sodium.

The formulations of the present invention may comprise one or more bleaching agents, such as one or more oxygen bleaches or one or more chlorine bleaching agents. Examples of suitable oxygen bleaching agents are anhydrous or sodium perborate, for example in the form of monohydrates or tetrahydrates or so-called dihydrates, anhydrous or sodium percarbonate, for example in the form of monohydrates, hydrogen peroxide, persulphates, Organic peracids (eg, peroxy lauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid) , 1,9-diperoxy sebacic acid, diperoxy isophthalic acid, in each case in the form of a free acid or in the form of an alkali metal salt, in particular in the form of a sodium salt, and also a sulfonium sulfonate Base peroxyacid and cationic peroxyacid).

The formulations of the present invention may comprise, for example, an oxygen bleach in the range of from 0.5% to 15% by weight.

Suitable chlorine bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhexylcarbazide, NN-chlorosulfonamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, Magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

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

The formulations of the present invention may comprise one or more bleaching catalysts. The bleaching catalyst may be selected from bleach-enhanced transition metal salts and/or transition metal complexes such as manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or manganese-, iron-, cobalt-, ruthenium. - or a molybdenum-carbonyl complex. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, as well as cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleaching catalyst.

The formulations of the present invention may comprise one or more bleach activators such as N-methylmorpholinium-acetonitrile salt ("MMA salt"), trimethylammonium acetonitrile salt, N-propylene sulfimide (eg N-oxime) Alkyl succinimide), 1,5-diethyl fluorenyl-2,2-dihydroxy hexahydro-1,3,5-triazine ("DADHT") or nitrile quat (Trimethylammonium acetonitrile salt).

Other examples of suitable bleach activators are tetraethylene ethylenediamine and tetraethylene hexamethylenediamine.

The formulations of the present invention may comprise one or more corrosion inhibitors. In the context of the present invention, this should be understood to mean the compounds which inhibit metal corrosion. Examples of suitable corrosion inhibitors are triazoles (specifically benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole), and also phenol derivatives (for example, hydroquinone, Catechol, hydroxy hydroquinone, gallic acid, phloroglucinol or pyrogallol).

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

The formulations of the present invention may comprise one or more detergents, such as sodium sulfate.

The formulations of the present invention may comprise one or more anti-foaming agents selected from, for example, polyoxalate oils and paraffinic oils.

In one embodiment of the invention, the formulations of the invention comprise a total of from 0.05% to 0.5% by weight of the anti-foaming agent.

In one embodiment of the invention, the formulations of the invention may comprise one or more acids, such as methane sulfonic acid.

In one embodiment of the invention, the pH of the formulation of the invention is in the range of from 5 to 14, preferably from 8 to 13.

The invention further provides for the use of the formulations of the invention for machine washing trays and kitchen utensils. In the context of the present invention, the kitchen utensils to be mentioned are, for example, pots, trays, casseroles, and metal objects (e.g., squeegees, fish knives, and garlic presses).

Preferably, the apparatus of the present invention is used to clean an object having at least one surface made of glass that may be decorated or undecorated. In this context, in the context of the present invention, a surface made of glass is understood to mean that the object has at least one portion made of glass which is in contact with the surrounding air and which can be soiled when the object is used. Thus, the objects may be made substantially the same as those of a drinking glass or glass bottle. However, it can also be, for example, a cover having individual components made of another material, such as a lid having an edge made of metal and a handle.

Surfaces made of glass may be decorated (eg, colored or embossed) or undecorated.

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 system uses a dishwasher wash (automatic dishwashing).

In one embodiment of the invention, at least one formulation of the invention is used in machine cleaning drinking glasses, bottles made of glass, and glass containers for cooking.

In one embodiment of the invention, the cleaning is carried out using water having a hardness in the range of 1 to 30° German hardness, preferably 2 to 25° German hardness, wherein the German hardness is specifically understood to mean calcium hardness.

If the formulation of the invention is used for machine cleaning, even when the machine is cleaned of an object having at least one surface made of glass, only a very low tendency to corrode towards the glass is observed, and as long as the cleaning together has at least one Objects made of glass and heavily soiled knives or pottery can be used. Moreover, cleaning the glass together with the formulations of the present invention is significantly less harmful than objects made from metal, such as with kettles, trays or garlic presses.

The invention further provides a process for the preparation of a formulation of the invention, also abbreviated as a process for the preparation of the invention. For carrying out the preparation process of the invention, the procedure may comprise, for example, mixing (eg, stirring) in one or more steps in the presence of water: (A) at least one member selected from the group consisting of aminocarboxylic acids and polyaminocarboxylic acids and a compound of a salt and a derivative, (B) at least one onium salt, (C) at least one homopolymer or copolymer of ethylenimine and optionally other components (D), and subsequently completely or at least partially removed water .

The compound (A), the phosphonium salt (B) and the polyethylenimine (C) are as defined above.

In an embodiment of the invention, before at least partially removing water, Mixing one or more other ingredients (D) of the formulation of the invention with, for example, one or more surfactants, one or more enzymes, one or more detergents (particularly phosphorus-free detergents), one or more a total detergent, one or more alkaline carriers, one or more bleaching agents, one or more bleaching catalysts, one or more bleach activators, one or more bleach stabilizers, one or more anti-foaming agents, or A variety of corrosion inhibitors, one or more detergents and buffers or dyes.

In one embodiment, the procedure comprises completely or partially removing water from the formulation of the invention (particularly by spray drying, spray granulation or compression) by evaporating (eg residual moisture in the range of 0 to 5 wt%) Inside).

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

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

The formulation of the present invention can be easily obtained by the preparation method of the present invention.

The cleansing formulations of the present invention may be provided in liquid or solid form, in single or multiphase, in the form of tablets or in other metering units, in encapsulated or unpackaged form. The water content of the liquid formulation can vary from 35% to 90% water.

The invention is illustrated by working examples.

General: After confirming the first cleaning of the test piece in a domestic dishwasher until the glass has been weighed and visually evaluated, the test piece is only treated with clean cotton gloves so as not to tamper with the weight and/or visual impression of the test piece.

Within the scope of the present invention, % and ppm are always % by weight and ppm by weight, unless otherwise specifically indicated, and in the case of the formulation of the invention Based on total solids content.

I. Preparation of the formulation of the invention Preparation of I.1 base mixture

First, a base mixture comprising the feed materials of Table 1 was prepared.

All quantitative data are expressed in g.

abbreviation: MGDA: methylglycine diacetate in the form of a trisodium salt

TAED: N, N, N', N'-tetraethylene ethylenediamine

HEDP: disodium salt of hydroxyethane (1,1-diphosphonic acid)

I.2 Preparation of the formulation of the invention

In a 100 ml beaker, introduce 20 ml of distilled water and continuously add the following materials with stirring: Table 2 铋 salt (B.1) or (B.2) or (B.3) or (B.4) or (B.5)

Table 2: Polyethylenimine (C.1), (C.2) or (C.3)

The mixture was stirred at room temperature for 10 minutes. Subsequently, MGDA trisodium salt (A.1) dissolved in 30 ml of water was added according to Table 2. This produces a distinctly clear solution. The base mixture of Table 2 was then added, the mixture was stirred again, and the water was evaporated.

This resulted in a formulation of the invention which was tested according to Table 2.

To prepare a comparative formulation, the procedure is similar except that the onium salt (B) or the polyethylenimine (C) or both are omitted.

During the immersion test, if the corresponding fraction of the base mixture is metered separately from the aqueous solution of (A.1), (B) or (C), the same amount of active ingredient is tested to obtain the same result. Therefore, the order of metering is not a problem.

(B.1) Barium nitrate: Bi(NO ₃ ) ₃ . 5H ₂ O

(B.2) Barium sulfate Bi ₂ (SO ₄ ) ₃

(B.3) cesium formate

(B.4) 叁Methanesulfonate

(B.5) Gallic acid bismuth The quantitative data of strontium salt is always based on 铋.

(C.1): Polyethylenimine homopolymer, M _w 800 g/mol, DB=0.63

(C.2): Polyethylenimine homopolymer, M _w 5000 g/mol, DB=0.67

(C.3): Polyethylenimine homopolymer, M _w 25 000 g/mol, DB=0.70

II. Use of the formulation of the invention and a comparative formulation for machine cleaning glass

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

II.1 Test Method Immersion Test

device: Stainless steel jug (approximately 6 liters in volume) with a perforated cover for contact with a thermometer

Screen base plug with mounting for stainless steel kettle

Magnetic stirrer with stirring rod, contact thermometer, perforated rubber stopper

Experimental conditions: Temperature: 75 ° C

Time: 72 hours

5 liters of distilled water or water with defined water hardness ("hardness water")

The test pieces used were in each case a champagne glass and brandy cup from Libbey (NL), material: soda lime glass.

Experimental procedure: For pretreatment purposes, first wash the test piece with 1 g of surfactant (nC ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH) and 1 g of citric acid in a domestic dishwasher (Bosch SGS5602) to remove Any contaminants. The test piece is dried, its weight is measured, and it is fixed to the screen substrate plug.

The stainless steel kettle was filled with 5.5 liters of water, and 25 g of the corresponding inventive formulation as in Table 3 was added, wherein Table 3 individually designated active components (A.1), as appropriate (B), depending on each case. Case (C) and a base mixture of the formulation of the invention or a comparative formulation. The cleaning liquid obtained in this manner was stirred at 550 rpm using a magnetic stirrer. A contact thermometer was installed and the stainless steel kettle was covered with a lid so that water could not be evaporated during the experiment. It was heated to 75 ° C and a screen substrate plug with two test pieces was placed in a stainless steel kettle to ensure that the test piece was completely submerged in the liquid.

At the end of the experiment, the test piece was removed and rinsed under running distilled water. The test piece consisting of 1 g of surfactant (nC ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH) and 20 g of citric acid was then used in a domestic dishwasher, and the test piece was washed again using a 55 ° C program to remove any Sediment.

To assess gravity wear, the dry test pieces were weighed. A visual assessment of the test piece is then carried out. For this purpose, the surface of the test piece was evaluated for wire corrosion (glass ridge) and atomization corrosion (slice atomization).

The evaluation was carried out according to the following scheme.

Wire corrosion:

L5: no visible line

L4: slightly formed lines in very few areas, micro-line corrosion

L3: Corrosion in several areas

L2: Corrosion in several areas

L1: severe line corrosion

Glass atomization

L5: no visible fog

L4: slight atomization in very few areas

L3: atomization in several areas

L2: atomization in several areas

L1: severely atomized on substantially the entire glass surface

Intermediate levels (eg L3-4) are also allowed during the assessment.

If hardness water having a 2°German hardness is used instead of water for testing, the formulations of the present invention are consistently superior to the corresponding comparative formulations in terms of inhibiting glass corrosion.

II.2 Results

The results are summarized in Table 2.

Claims (14)

A formulation comprising (A) at least one compound selected from the group consisting of aminocarboxylic acids and polyaminocarboxylic acids, (B) at least one bismuth (Bi) salt, (C) homopolymerization of at least one exoethylamine Or a copolymer. The formulation of claim 1 which is free of phosphates and polyphosphates. The formulation of claim 1 or 2, wherein (C) is selected from the group consisting of a linear or branched homopolymer of exoethylimine and a graft copolymer of ethylenimine. The formulation of claim 1 or 2 wherein the onium salt (B) is selected from the group consisting of barium gallate and barium methanesulfonate. The formulation of claim 1 or 2, wherein the compound (A) is selected from the group consisting of methyl glycine diacetic acid (MGDA), nitrogen triacetic acid, and glutamic acid diacetic acid, and salts and derivatives thereof. A formulation according to claim 1 or 2 which is solid at room temperature. A formulation according to claim 1 or 2 which comprises water in the range from 0.1% to 10% by weight. The formulation of claim 1 or 2, which comprises: compound (A) in total in the range of 0.05% by weight to 1% by weight, water-soluble Bi salt in the range of 0.05% by weight to 0.3% by weight in total, 0 to total A homopolymer or copolymer of from 0.05% to 2% by weight of the ethylenimine is in each case based on the solids content of the formulation. Use of a formulation according to any one of claims 1 to 8 for the washing of pottery, knives and kitchen utensils. Use of a formulation according to any one of claims 1 to 8 for washing an object having at least one surface made of glass which may be decorated or undecorated. The use of claim 9 or 10, wherein the washing is performed using a dishwasher. The use of claim 9 or 10, wherein at least one of the formulations of any one of claims 1 to 8 is used for washing a drinking glass, a glass bottle and a glass container for cooking. A process for the preparation of a formulation according to any one of claims 1 to 8, wherein (A) at least one compound selected from the group consisting of aminocarboxylic acids and polyaminocarboxylic acids, (B) at least one phosphonium salt, (C) Optionally, at least one homopolymer or copolymer of ethylenimine and optionally other components are mixed with each other in the presence of water in one or more steps, and the water is subsequently removed. The method of claim 13, wherein the water is removed by spray drying.