TW201321498A - Formulations, their use as or for producing dishwashing detergents and their production - 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, (B) at least one homopolymer or copolymer of ethyleneimine, c sodium citrate and (D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.

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 an aminocarboxylic acid and a polyaminocarboxylic acid, (B) a homopolymer or copolymer of at least one ethylenimine, (C) Sodium citrate and (D) at least one compound selected from the group consisting of alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.

Furthermore, the invention relates to a process for the manufacture of a formulation according to the invention and to its use as or for the manufacture of dishwashing detergents, in particular dishwashing detergents for machine dishwashing.

Dishwashing must meet many requirements. For example, it must thoroughly clean the tray, which should be free of harmful or potentially harmful substances in the waste water, which should allow water to flow out of the tray and dry, and which should not cause problems during dishwasher operation. Finally, it should not result in an aesthetically undesired result on the item to be cleaned. In this regard, glass corrosion is specifically 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 primarily promoted by chemical influences. For example, certain ions may elute from the glass due to repeated machine washing, which adversely alters optical properties and thereby alters aesthetic properties.

Several effects were observed in the case of glass corrosion. First, the formation of microscopic fine lines, which are noticeable in the form of lines, can be observed. Second, in many situations Underneath, general atomization, such as roughening, can be observed which makes the glass seem unattractive. This type of effect is also subdivided into rainbow-colored fading, scratching, and plaque and ring turbidity.

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. Zinc and zinc-containing dishwashing detergents lose confidence. However, in many cases, glass corrosion, specifically line corrosion and turbidity, 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 method of making 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 referred to as formulations of the invention.

The formulations according to the invention comprise (A) at least one compound selected from the group consisting of aminocarboxylic acids and polyaminocarboxylic acids (also referred to in the context of the invention as aminocarboxylic acids (A) or polyaminocarboxylic acids (A). Or the compound (A)) and its derivatives and preferred salts.

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⁺ , preferably 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 nitrilotriacetic acid and their organic compounds having a tertiary amine group having one or two CH ₂ -COOH groups A group which 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.

Preferably, the polyaminocarboxylic acid (A) is selected from the group consisting of 1,2-diaminoethanetetraacetic acid, tetraethylenemethylidenediamine, tetraethylenephosphonium hexamethylenediamine, and imidodisuccinic 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 nitrilotriacetic acid and they have an organic compound based on an amino acid structure, and the amino group of the amino acid 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), nitrilotriacetic 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 additionally comprise (B) at least one homopolymer of ethylenamine, also collectively referred to as polyethylenimine (B).

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

In one embodiment of the invention, the average molecular weight M _w of the polyethylenimine (B), 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 (B) is selected from the group consisting of highly branched polyethylenimines. The highly branched polyethylenimine (B) 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 (B) 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 (B).

In the context of the present invention, the dendritic polyethylenimine (B) has a structurally and molecularly homogeneously structured polyethylenimine (B).

In one embodiment of the invention, the polyethylenimine (B) 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 (B) 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.

The formulations of the invention additionally comprise sodium citrate (C). The term sodium citrate herein includes monosodium salts and preferably disodium salts. Sodium citrate can be used in the form of an anhydrous salt or in the form of a hydrate (for example in the form of a dihydrate).

The formulations of the present invention additionally comprise (D) at least one compound selected from the group consisting of alkali metal percarbonates, alkali metal perborates and alkali metal persulfates, also referred to as "bleach (D)" within the scope of the present invention.

Preferred bleaching agents (D) are selected from anhydrous or sodium perborate, for example in the form of a monohydrate or in the form of a tetrahydrate or so-called dihydrate, anhydrous or sodium percarbonate, for example in the form of a monohydrate, and sodium persulfate. Wherein the term "persulfate" in each case includes both peracid H ₂ SO ₅ salts and peroxodisulfates.

In this connection, the alkali metal salt may also be an alkali metal hydrogencarbonate, an alkali metal perborate or an alkali metal persulfate in each case. However, in each case, the dialkali metal salt is preferred.

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 2% by weight. The homopolymer (B) of ethylimine, preferably 0.1% by weight to 0.5% by weight, 1% by weight to 50% by weight of sodium citrate (C), preferably 5% by weight to 30% by weight, with anhydrous lemon a total of 0.5% to 15% by weight of bleach (D) selected from the sodium form, selected from the group consisting of alkali metal percarbonates, alkali metal perborates and alkali metal persulphates, in each case based on The solid content of the formulation is described.

In one embodiment of the invention, the formulations of the invention are solid at room temperature, 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.

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

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 strontium compounds. By "free" heavy metal compounds it is to be understood in the context of the present invention to mean that the total content of heavy metal compounds which do not have a bleaching catalyst effect is in the range from 0 to 100 ppm according to the Leach method.

In the context of the present invention, "heavy metals" are all metals having a specific density of at least 6 g/cm ³ . Specifically, heavy metal precious metals are also zinc, antimony, iron, copper, lead, tin, nickel, cadmium, and chromium.

Preferably, the formulations of the present invention comprise non-measurable parts of zinc and bismuth compounds, i.e., less than 1 ppm.

In one embodiment of the invention, the formulation of the invention may have other ingredients (E), such as one or more surfactants, one or more enzymes, one or more synergists, specifically phosphorus-free synergies. Agent, one or more co-boosting agents, 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 antifoaming agents Agent, one or more corrosion inhibitors, one or more synergists, buffers, dyes, one or more fragrances, one or more organic solvents, one or more tableting aids, one or more disintegrants, one or more A thickener 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 ^{1 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 c 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 oxides 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 formulation of the invention may comprise 3 weights Surfactants ranging from % 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, based in each case on the total solids content of the formulation according to the invention.

In addition to sodium citrate, the formulations of the invention may also comprise one or more synergists, in particular phosphate-free synergists. Examples of suitable builders 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 also fatty acid sulfonates, α-hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl dians Acid salts, tartaric acid diacetates, tartaric acid monoacetates, oxidized starches, and polymeric synergists (eg, polycarboxylates and polyaspartic acid).

In one embodiment of the invention, the synergist is selected from the group consisting of polycarboxylates such as (meth)acrylic acid homopolymers or alkali metal salts of (meth)acrylic acid copolymers.

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, ethoxypolypropylene glycol (Meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxy 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 Alkene Propyloxybenzenesulfonic acid, methylallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid , styrenesulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethyl decylamine, sulfomethylmethyl Acrylamide, and salts of such acids (eg, sodium, potassium or ammonium salts thereof).

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

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

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 synergist.

In one embodiment of the invention, the formulations of the invention may comprise one or more co-boosting agents.

Examples of co-boosting agents are phosphonates such as hydroxyalkanephosphonates and alkane alkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a co-booster. It is preferably used in the form of a sodium salt, the disodium salt produces a neutral reaction and the tetrasodium salt produces an alkaline reaction (pH 9). Suitable amino alkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriamine penta methylene phosphonate (DTPMP) and higher carbon number analogs thereof. 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 ensures, 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, especially the system sodium.

In addition to bleach (D), the formulations of the present invention also comprise one or more chlorine bleaches.

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 can be selected from bleach-enhanced transition metal salts or transition metal complexes such as manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. 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).

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 include 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 synergistic substances, 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.

The formulations of the present invention may comprise a phosphonic acid or one or more phosphonic acid derivatives, such as hydroxyethane-1,1-diphosphonic acid.

The invention further provides for the use of the formulations of the invention for machine cleaning trays and kitchen appliances. Within the scope of the present invention, kitchen appliances such as pots, trays, casseroles, and objects made of metal (e.g., shovel, fish knife and garlic press) may be mentioned.

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 ambient 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 different materials, such as a lid having a metal-made edge and a handle.

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

The term "glass" includes any desired type of 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 a machine for cleaning drinking glass, glass bottles 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 in the case of repeated machine cleaning of objects having at least one surface made of glass, only a very low tendency to corrode towards the glass is observed, and as long as there is at least one cleaning together An object made of glass and a heavily soiled knife or plate. 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.

In addition, it has been observed that the formulations of the present invention have excellent bleaching effects when used on wash trays and kitchen utensils and glass surfaces.

The invention further provides a method of making a formulation of the invention, also referred to as a manufacturing method of the invention. To practice the method of manufacture of the present invention, the procedure can include, for example, rendering (A) at least one member selected from the group consisting of aminocarboxylic acids and polyaminocarboxylic acids and salts thereof in one or more steps in the presence of water. a compound of the compound, (B) at least one phosphonium salt, (C) at least one homopolymer or copolymer of ethylenimine and optionally other components (E) are mixed with each other (for example, stirred), and then completely or At least partially remove water.

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

In one embodiment of the invention, one or more of the other components (E) of the formulation of the invention may be mixed with, for example, one or more surfactants, one or more enzymes, one or more, prior to at least partial removal of water. a synergist, one or more co-boosting agents (specifically, a phosphorus-free synergist), 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, one or more corrosion inhibitors, one or more synergists and a buffer or dye.

In one embodiment, the procedure comprises removing water completely or partially therefrom by evaporation of the formulation of the invention, in particular by spray drying, spray granulation or compression (eg residual moisture in the range of 0 to 5% by weight) ).

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 production method of the present invention.

The cleansing formulations of the present invention may be provided in liquid or solid form, in single or multi-phase, in the form of tablets or in other dosage 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.

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

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. Dry the mixed feed material.

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, 20 ml of distilled water was introduced as the initial charge and the following materials were continuously added under stirring: the polyethylenimine (B.1), (B.2), (B) of Table 2 (or 3) .3), (B.4) or (B.5)

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 (or 3). This produces a distinctly clear solution. The base mixture was then added according to Table 2 (or 3), 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 (or 3).

For the preparation of comparative formulations, the procedure is similar except that the polyethylenimine (B) or the copolymer of exoethylenimine is omitted.

In the test "Using a continuously operated dishwasher" (or in an immersion test), if the corresponding fraction of the base mixture is in combination with (A.1), (B), (C.1) or (D.1) aqueous solution Separately metered, the same results were obtained with dry formulations tested to have the same amount of active ingredient. Therefore, the order in which the measurements are added is not important.

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

(B.2): Polyethylenimine homopolymer, M _w 2000 g/mol, DB=0.64

(B.3): Polyethylenimine homopolymer, M _w 5000 g/mol, DB=0.67

(B.4): Polyethylenimine homopolymer, M _w 25 000 g/mol, DB=0.7

(B.5): Polyethylenimine homopolymer, M _w 750 000 g/mol, DB=0.69

(B.6) Polyethylenimine, ethoxylated

(B.7) Polyethylenimine, carboxymethylated, sodium salt, 80 mol% functionalized with a primary amine group, M _w 50 000 g/mol (after carboxymethylation)

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 using a dishwasher that operates continuously

Dishwasher: Miele G 1222 SCL

Program: 65 ° C (pre-wash)

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

For cleaning, the cups are placed in a ceramic basket above the dishwasher. The dishwashing detergent used in each case is 25 g of the formulation of the invention or the comparative formulation of Table 2, wherein Table 2 individually specifies the active ingredient (A.1) of the formulation of the invention in each case, Base mixture (including (C.1) and (D.1) and optionally (B)). The washing was carried out at a cleaning-rinsing temperature of 55 °C. In each case, the water hardness is in the range of 0 to 2 ° German hardness. Washing was carried out for 100 wash cycles in each case, even though the program was run 100 times. After 100 washing cycles, the evaluation was carried out by measuring the weight and visually.

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

In addition to the gravity evaluation, the appliance was visually evaluated using a grading scale of 1 (very poor) to 5 (excellent) after 100 cycles in the darkroom and after the post-perforation of the multiwell plate. In this regard, the level of plaque corrosion/turbidity and/or line corrosion is determined in each case.

II.2 Test method for immersion test

device:

Stainless steel jug (about 6 liters in volume) with a perforated cover mesh base plug for contact with a thermometer, with a magnetic stirrer for a stainless steel kettle with a stir bar, 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 body used was in each case a champagne glass from Libbey (NL) and a brandy glass, material: soda lime glass.

Experimental procedure:

For pretreatment purposes, the test body was first washed with 1 g of surfactant (nC ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH) and 20 g of citric acid in a domestic dishwasher (Bosch SGS5602) to remove any dirt. . The test body was dried, its weight was measured, and it was fixed to the grid substrate plug.

Fill the stainless steel kettle with 5.5 liters of water and add 25 g of the formulation of the invention or a comparative formulation; Table 3 individually specifies the active component (A.1), as appropriate (B), as appropriate (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 grid substrate plug with two test bodies was inserted into a stainless steel kettle to ensure that the test body was completely submerged in the liquid.

At the completion of the experiment, the test body was taken out and rinsed under running distilled water. The test body 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 body was again washed with a 55 ° C program to remove any Sediment.

To assess gravity wear, the dry test body was weighed. Subsequent testing Visual assessment of the specimen. For this purpose, the surface of the test body was evaluated for wire corrosion (rope) and turbid corrosion (spotted turbidity).

The assessment was carried out according to the following scheme.

Wire corrosion:

L5: no obvious line

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

L3: Line corrosion in some areas

L2: line corrosion in multiple areas

L1: protruding line corrosion

Glass turbid

L5: no obvious turbidity

L4: slight turbidity in very few areas

L3: turbid in some areas

L2: turbid in multiple areas

L1: turbid on the entire surface of the glass

Intermediate levels (eg L3-4) are also allowed in the case of inspections.

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 with respect to inhibiting glass corrosion.

II.3 Results

The results are summarized in Tables 2 and 3.

Claims (14)

A formulation comprising (A) at least one compound selected from the group consisting of aminocarboxylic acids and polyaminocarboxylic acids, and (B) at least one ethyleneimine homopolymer, (C) sodium citrate and (D) At least one compound selected from the group consisting of alkali metal percarbonate, alkali metal perborate and alkali metal persulfate. The formulation of claim 1 which is free of phosphates and polyphosphates. A formulation according to claim 1 or 2 wherein (B) is selected from the group consisting of linear and branched homopolymers of ethylenimine. The formulation of claim 1 or 2 having a heavy metal content of less than 0.05 ppm based on the solids content of the formulation. The formulation of claim 1 or 2, wherein the compound (A) is selected from the group consisting of methylglycine diacetic acid (MGDA), nitrilotriacetic 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 of from 0.1% by weight to 10% by weight. A formulation according to claim 1 or 2, which comprises: a total of from 1% by weight to 50% by weight of the compound (A), and a total of from 0.05% by weight to 2% by weight of the extended ethylimine homopolymer (B) sodium citrate (C) in the range of 1% by weight to 50% by weight and the compound (D) in the range of 0.5% by weight to 15% by weight in total, In each case it is based on the solids content of the formulation. Use of a formulation according to any one of claims 1 to 8 for a washing tray and a kitchen appliance. 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 vessel for cooking. A method of producing 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 ethylidene imine a homopolymer, (C) sodium citrate and (D) at least one compound selected from the group consisting of alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, and optionally other components in one or more steps The medium is mixed with each other in the presence of water, and then the water is removed. The method of claim 13, wherein the water is removed by spray drying.