EP2768936B1 - Formulations, their use as or for the manufacture of dishwashing compositions, and manufacture - Google Patents

Formulations, their use as or for the manufacture of dishwashing compositions, and manufacture Download PDF

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Publication number
EP2768936B1
EP2768936B1 EP12770153.0A EP12770153A EP2768936B1 EP 2768936 B1 EP2768936 B1 EP 2768936B1 EP 12770153 A EP12770153 A EP 12770153A EP 2768936 B1 EP2768936 B1 EP 2768936B1
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EP
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Prior art keywords
bismuth
acid
formulations
range
ethyleneimine
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EP12770153.0A
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German (de)
French (fr)
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EP2768936A1 (en
Inventor
Stephan Hüffer
Markus Hartmann
Sonja Fischer
Stefan Fassbender
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2096—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers

Definitions

  • the present invention relates to a process for the preparation of formulations according to the invention and their use as or for the production of dishwashing detergents, in particular dishwashing detergents for machine dishwashing.
  • Dishwashing detergents have many requirements to fulfill. So they have to clean the dishes thoroughly, they should have no harmful or potentially harmful substances in the wastewater, they should allow the draining and drying of the water from the dishes, and they should not cause problems when operating the dishwasher. Finally, they should not lead to aesthetically undesirable consequences on the good to be cleaned. Especially in this context is the glass corrosion.
  • Glass corrosion is caused not only by mechanical effects, for example by rubbing glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences.
  • certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.
  • Glass corrosion has several effects. On the one hand, one can observe the formation of microscopically fine cracks, which are noticeable in the form of lines. On the other hand, in many cases one can observe a general cloudiness, for example a roughening, which makes the glass in question look unaesthetic. Overall, such effects are also subdivided into iridescent discoloration, scoring and surface and annular opacities.
  • Dishwashing agents which contain polyethyleneimine. Such dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion. Zinc and bismuth-containing dishwashing detergents are not recommended.
  • the glass corrosion in particular the line corrosion and the turbidity, but is not sufficiently delayed or prevented in many cases.
  • formulations defined above were found, also called formulations according to the invention.
  • (A) in total in the range of 1 to 50% by weight of at least one compound selected from aminocarboxylates and polyaminocarboxylates in the context of the present invention also briefly aminocarboxylate (A) or polyarrminocarboxylate (A) or compound (A) called, and their derivatives and preferably salts.
  • Compound (A) may be in the form of a free acid or preferably in partially or completely neutralized form, ie as a salt.
  • counterions for example inorganic cations, such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, more preferably Na +, K +, or organic cations, preferably substituted with one or more organic radicals ammonium, in particular triethanol ammonium, 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.
  • compound (A) is selected from derivatives of aminocarboxylates and polyaminocarboxylates, for example methyl or ethyl esters.
  • aminocarboxylates (A) are understood as meaning nitrilotriacetic acid and those organic compounds which have a tertiary amino group which has one or two CH 2 -COOH groups which, as mentioned above, can be partially or completely neutralized or can.
  • polyaminocarboxylates (A) are understood as meaning those organic compounds which have at least two tertiary amino groups which independently of one another have one or two CH 2 -COOH groups which, as mentioned above, can be partially or completely neutralized or can.
  • aminocarboxylates (A) are selected from those organic compounds having a secondary amino group having one or two CH (COOH) CH 2 -COOH group (s) partially as mentioned above or can be completely neutralized.
  • polyaminocarboxylates (A) are selected from those organic compounds having at least two secondary amino groups each containing a CH (COOH) CH 2 -COOH group which, as mentioned above, partially or completely neutralizes could be.
  • Preferred polyaminocarboxylates (A) are selected from 1,2-diaminoethanetetraacetic acid, iminodisuccinate (IDS), diethylenetriamine pentaacetate (DTPA), hydroxyethylenediaminetriacetate (HEDTA), and their respective salts, most preferably the alkali metal salts, especially the sodium salts.
  • Preferred aminocarboxylates (A) and polyaminocarboxylates (A) are nitrilotriacetic acid and those organic compounds having an amino acid-based structure whose amino group (s) have one or two CH 2 -COOH groups and are tertiary amino groups. It is possible to select amino acids from L-amino acids, R-amino acids and mixtures of enantiomers of amino acids, for example the racemates.
  • compound (A) is selected from methylglycine diacetate (MGDA), nitrilotriacetic acid and glutamic acid diacetate and their derivatives and preferably their salts, in particular their sodium salts. Very particular preference is given to methylglycine diacetate and to the trisodium salt of MGDA.
  • formulations according to the invention contain in the range from 0.05 to 0.4% by weight of at least one salt of bismuth (B).
  • Salts of bismuth (B) can be selected from water-soluble and non-water-soluble salts of bismuth.
  • such salts of bismuth (B) are said to be insoluble in water and are distilled in water Water at 25 ° C have a solubility of 0.1 g / l or less.
  • Salts of bismuth (B) which have a higher water solubility, are accordingly referred to in the context of the present invention as water-soluble salts of bismuth.
  • bismuth (B) salt is selected from bismuth acetate, bismuth nitrate, bismuth sulfate, bismuth tri-formate ("bismuth formate"), bismuth gallate and bismuth trismethanesulfonate, preferably bismuth gallate and bismuth trismethanesulfonate.
  • salt of bismuth (B) is selected from Bi 2 O 3 , Bi 2 O 3 ⁇ aq, BiO (OH). Preference is given to BiO (OH).
  • salt of bismuth (B) is selected from bismuth oxides having an average particle diameter (weight average) in the range of 10 nm to 100 ⁇ m.
  • the cation in salt of bismuth (B) can be complexed, for example, complexed with ammonia ligands or with water ligands, and in particular be present hydrated.
  • ligands are usually omitted in the context of the present invention, if they are water ligands.
  • salt of bismuth (B) can be converted. It is thus possible, for example, to use bismuth acetate or BiCl 3 for the preparation of the formulation according to the invention, but at a pH of 8 or 9 in an aqueous environment to form BiO (CH 3 COO) or BiOCl, BiO (OH) or Bi 2 O 3 ⁇ aq converts, which may be present in uncomplexed or complexed form.
  • Salt of bismuth (B) is present in such formulations according to the invention which are solid at room temperature, preferably in the form of particles, for example having a mean diameter (number average) in the range of 10 nm to 100 ⁇ m, preferably 100 nm to 5 ⁇ m, determined, for example, by X-ray scattering.
  • Salt of bismuth (B) is present in such formulations according to the invention, which are liquid at room temperature, in dissolved or in solid or in colloidal form.
  • Formulation according to the invention furthermore contains (C) in the range from 0.05 to 2% by weight in total of at least one copolymer or preferably a homopolymer of ethyleneimine, together referred to in short as polyethyleneimine (C).
  • copolymers of ethyleneimine also include copolymers of ethyleneimine (aziridine) with one or more higher homologues of ethyleneimine, such as propyleneimine (2-methylaziridine), 1- or 2-butylenimine (2-ethylaziridine or Dimethylaziridine), for example, with 0.01 to 75 mol% of one or more Homologs of ethyleneimine, based on the proportion of ethyleneimine.
  • ethyleneimine ethyleneimine
  • aziridine ethyleneimine
  • 2-butylenimine 2-ethylaziridine or Dimethylaziridine
  • copolymers of ethyleneimine (C) are selected from graft copolymers of ethyleneimine (C). Such graft copolymers are in
  • ethyleneimine graft copolymers (C) are selected from those polymers obtainable by grafting polyamidoamines with ethyleneimine.
  • ethyleneimine graft copolymers (C) are composed of 10 to 90% by weight of polyamidoamine as grafting base and 90 to 10% by weight of ethyleneimine as grafting support, each based on ethyleneimine graft copolymer (C).
  • Polyamidoamines are obtainable for example by condensation of polyalkylenepolyamines in pure form, as a mixture with one another or in a mixture with diamines.
  • polyalkylenepolyamines are understood as meaning compounds which contain at least 3 basic nitrogen atoms in the molecule, for example diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N- (2-aminoethyl) -1,3-propanediamine and N , N'-bis (3-aminopropyl) ethylenediamine.
  • diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, isophoronediamine, 4,4'-diaminodiphenylmethane, 1,4-bis ( 3-aminopropyl) piperazine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine and ⁇ , ⁇ -diamino compounds of polyalkylene oxides.
  • ethyleneimine graft copolymers (C) are selected from those polymers which can be prepared by grafting polyvinylamines as a grafting base with ethyleneimine or oligomers of ethyleneimine, for example dimerren or trimers of ethyleneimine.
  • ethyleneimine graft copolymers (C) are composed of 10 to 90% by weight of polyvinylamine as grafting base and 90 to 10% by weight of ethyleneimine as grafting support, in each case based on ethyleneimine graft copolymer (C).
  • At least one polyethyleneimine (C) in the form of a homopolymer, preferably uncrosslinked, is chosen as the component of the formulation according to the invention.
  • polyethyleneimine (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.
  • polyethyleneimine (C) has an average molecular weight M w 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, determinable for example by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • polyethyleneimines (C) are selected from highly branched polyethyleneimines. Highly branched polyethyleneimines (C) are characterized by their
  • polyethyleneimines (C) are selected from highly branched polyethyleneimines.
  • Highly branched polyethylenimines (C) are characterized by their high degree of branching (DB).
  • Polyethyleneimines (C) having DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90 and more preferably in the range from 0.30 to 0.80%, are considered highly branched polyethylenimines (C) within the scope of the present invention. and most preferably at least 0.5.
  • polyethylene dendrimers (C) which are dendritic polyethylenimines (C) are understood as meaning polyethylenimines (C) having a structurally and molecularly uniform structure.
  • polyethylenimine (C) is highly branched polyethyleneimines (homopolymers) having an average molecular weight M w in the range from 600 to 75,000 g / mol, preferably in the range from 800 to 25,000 g / mol.
  • polyethylenimine (C) is highly branched polyethyleneimines (homopolymers) 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 is selected from dendrimers.
  • compound (A) in total in the range from 1 to 50% by weight of compound (A), preferably from 10 to 25% by weight, in total in the range from 0.05 to 0.4% by weight of bismuth (B) salt, preferably 0, 1 to 0.2 wt .-%, and a total of from 0.05 to 2% by weight of homopolymer or copolymer of ethyleneimine (C), preferably from 0.1 to 0.5% by weight, in each case based on solids content of the relevant formulation.
  • B bismuth
  • C homopolymer or copolymer of ethyleneimine
  • the proportion of salt of bismuth is given as bismuth or bismuth ions.
  • the formulation according to the invention is a granulate, a liquid preparation or a gel.
  • salts of bismuth (B) may be present in formulations of the invention complexed by polyethylenimine (C).
  • the formulation according to the invention contains from 0.1 to 10% by weight of water, based on the sum of all solids of the relevant formulation.
  • formulation according to the invention is free of phosphates and polyphosphates, wherein hydrogen phosphates are subsumed, for example, free of trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate.
  • free from in connection with phosphates and polyphosphates in the context of the present invention should be understood to mean that the total content of phosphate and polyphosphate ranges from 10 ppm to 0.2% by weight, determined by gravimetry.
  • the formulation of the present invention is free of those heavy metal compounds which do not function as bleach catalysts, especially compounds of iron and zinc.
  • "free from” is to be understood in connection with heavy metal compounds as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in the range from 0 to 100 ppm, preferably from 1 to 30 ppm, determined according to Leach method.
  • heavy metals are all metals having a specific density of at least 6 g / cm 3 , but not bismuth.
  • the heavy metals are precious metals and zinc, iron, copper, lead, tin, nickel, cadmium and chromium.
  • formulation of the invention contains no measurable levels of zinc compounds, that is, for example, less than 1 ppm.
  • formulation according to the invention may comprise further ingredients (D), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more a plurality of bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more perfumes, one or more organic solvents, one or more several tableting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizing agents.
  • D further ingredients
  • surfactants are, in particular, nonionic surfactants and mixtures of anionic or zwitterionic surfactants with nonionic surfactants.
  • Preferred nonionic surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.
  • Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
  • these may be block copolymers or random copolymers, preference being given to block copolymers.
  • suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide.
  • suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters.
  • amine oxides or alkyl glycosides are also suitable.
  • anionic surfactants are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates having one to six ethylene oxide units per molecule.
  • formulation of the invention may contain in the range of from 3 to 20% by weight of surfactant.
  • Formulations of the invention may contain one or more enzymes.
  • enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
  • Formulations according to the invention may contain, for example, up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, in each case based on the total solids content of the formulation according to the invention.
  • Formulations according to the invention may contain one or more builders, in particular phosphate-free builders.
  • suitable builders are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, especially those of the formula ⁇ -Na 2 Si 2 O 5 , ⁇ -Na 2 Si 2 O 5 , and ⁇ -Na 2 Si 2 O 5 , furthermore citric acid and their alkali metal salts, succinic acid and its alkali metal salts, fatty acid sulfonates, ⁇ -hydroxypropionic acid, alkali malonates, Fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders such as polycarboxylates and polyaspartic acid.
  • builders of polycarboxylates are selected, for example, alkali metal salts of (meth) acrylic acid homo- or (meth) acrylic acid copolymers.
  • Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
  • a suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 2000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
  • monomers selected from the group consisting of 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 with at least one hydrophilic or hydrophobically modified monomers are used as 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, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexadecene and 1-octadecene.
  • Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples which may be mentioned are: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate , Ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate.
  • Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
  • Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2 hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, Styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and salts of
  • Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.
  • amphoteric polymers can also be used as builders.
  • Formulations according to the invention may contain, for example, in the range from 10 to 50% by weight, preferably up to 20% by weight, of builder.
  • Formulations of the invention may contain one or more co-builders.
  • co-builders are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • Formulations of the invention may contain one or more alkali carriers.
  • Alkaline carriers for example, provide the pH of at least 9 when an alkaline pH is desired.
  • Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates.
  • Preferred alkali metal is in each case potassium, particularly preferred is sodium.
  • Formulations of the invention may contain one or more bleaches, for example, one or more oxygen bleaches, or one or more chlorine-containing bleaches.
  • oxygen bleaching agents are sodium perborate, anhydrous or, for example, monohydrate or tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy- ⁇ -naphthoic acid, 1,12-diperoxydodecanedioic acid , Perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as the free acid or as the alkali metal salt, in particular as the sodium salt, furthermore sulfonyl peroxyacids and cationic peroxyacids.
  • formulations according to the invention may contain in the range of 0.5 to 15% by weight of oxygen bleach.
  • Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.
  • formulations according to the invention may contain in the range of from 3 to 10% by weight of chlorine-containing bleach.
  • Formulations of the invention may contain one or more bleach catalysts.
  • Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes.
  • Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.
  • Formulations of the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts”), trimethyl ammonium acetonitrile salts, N-acylimides such as N-nonanoyl succinimide, "1,5-diacetyl-2,2-dioxohexahydro-1,3 , 5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • MMA salts N-methylmorpholinium acetonitrile salts
  • DADHT 5-triazine
  • nitrile quats trimethylammonium acetonitrile salts
  • bleach activators are tetraacetylethylenediamine and tetraacetylhexylenediamine.
  • Formulations of the invention may contain one or more corrosion inhibitors.
  • corrosion inhibitors such compounds that inhibit the corrosion of metal.
  • suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
  • formulations according to the invention contain a total of in the range of 0.1 to 1.5 wt .-% corrosion inhibitor.
  • Formulations of the invention may contain one or more builders, for example, sodium sulfate.
  • Formulations of the invention may contain one or more defoamers selected, for example, from silicone oils and paraffin oils.
  • formulations according to the invention contain in total in the range from 0.05 to 0.5% by weight defoamer.
  • formulations according to the invention may contain one or more acids, for example methanesulfonic acid.
  • formulations according to the invention have a pH in the range from 5 to 14, preferably 8 to 13.
  • Another object of the present invention is the use of formulations according to the invention for the automatic cleaning of dishes and kitchen utensils.
  • kitchen utensils in the context of the present invention, for example, pots, pans, casseroles to call, and metal objects such as, for example, skimmers, roasters and garlic presses.
  • a surface of glass is to be understood as meaning that the object in question has at least one piece of glass which comes into contact with the ambient air and can be contaminated when the object is used.
  • the objects in question may be those which are essentially glassware such as drinking glasses or glass bowls. But it can also be, for example, cover that have individual components of a different material, such as pot lid with edging and metal handle.
  • Glass surface may be decorated, for example colored or printed, or not decorated.
  • glass includes any glass, for example lead glass and in particular soda lime glass, crystal glass and borosilicate glasses.
  • Machine cleaning is preferably dishwashing with a dishwasher (English: automatic dishwashing).
  • At least one formulation according to the invention for automated cleaning of drinking glasses, glass vases and glass jars is used for cooking.
  • water having a hardness in the range from 1 to 30 ° dH, preferably from 2 to 25 ° dH, is used for cleaning, German hardness being taken to mean in particular the calcium hardness.
  • formulations according to the invention for machine cleaning, it is observed even with repeated mechanical cleaning of objects which have at least one surface made of glass, only very slight tendency to glass corrosion, and even when you clean objects that have at least one surface of glass together with heavily soiled cutlery or dishes. In addition, it is much less harmful to use the formulation of the present invention to clean glass together with metal objects, such as pots, pans or garlic presses.
  • Compound (A), salt of bismuth (B) and polyethyleneimine (C) are defined above.
  • one or more surfactants for formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus free builder, one or more co-builders, one or more alkali carriers, one or more bleaches, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders Buffer or dye.
  • the water is removed completely or partially, for example to a residual moisture in the range from zero to 5% by weight, from the formulation according to the invention by evaporation, in particular by spray drying, spray granulation or compaction.
  • the water is removed, in whole or in part, at a pressure in the range of 0.3 to 2 bar.
  • the water is removed, in whole or in part, at temperatures in the range of 60 to 220 ° C.
  • the cleaning formulations according to the invention can be provided in liquid or solid form, single- or multiphase, as tablets or in the form of other dosage units, packaged or unpackaged.
  • the water content of liquid formulations can vary from 35 to 90% water.
  • % and ppm always denote wt .-% and wt ppm, if not expressly stated otherwise, and in the case of formulations according to the invention based on the total solids content.
  • Base mixtures were prepared containing the feedstocks according to Table 1.
  • Table 1 Basic mixtures for experiments with formulations according to the invention and comparative formulations
  • Base 1 Base 2
  • Base 3 protease 2.5 2.5 2.5 amylase 1 1 1 nC 18 H 37 (OCH 2 CH 2 ) 9 OH 5 5
  • Polyacrylic acid M w 4,000 g / mol as sodium salt, completely neutralized 10 10 10 sodium 10.5 10.5 10.5 TAED 4 4 4 Na 2 Si 2 O 5 2 2 2 Na 2 CO 3 19.5 19.5 19.5 Sodium citrate dihydrate 0 22.5 30 HEDP 0.5 0.5 0.5 All quantities in g.
  • test specimens were each a champagne glass and a shot glass from the company Libbey (NL), a, material: soda-lime glasses.
  • test pieces were rinsed in a domestic dishwasher (Bosch SGS5602) with 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 1 g of citric acid to remove any impurities.
  • the test pieces were dried, their weight determined and fixed on the grid floor insert.
  • the stainless steel pot was filled with 5.5 liters of water and added 25 g of the corresponding formulation according to the invention according to Table 3, where Table 3 shows the active components (A.1), optionally (B), optionally (C) and base mixture of formulation according to the invention or Comparison formulation individually specified.
  • the resulting cleaner liquor was stirred by means of the magnetic stirrer at 550 revolutions per minute. They installed the contact thermometer and covered the stainless steel pot with the lid, so that no water could evaporate during the experiment. It was heated to 75 ° C and put the grid bottom insert with the two specimens in the stainless steel pot, taking care that the specimens were completely immersed in the liquid.
  • test pieces were taken out and rinsed under running distilled water. Thereafter, the test pieces were rinsed in the domestic dishwasher with a formulation consisting of 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g of citric acid again with the 55 ° C program to remove any deposits ,
  • the dry specimens were weighed. This was followed by the visual assessment of the test specimens. Here one judged the surface use with the two specimens in the stainless steel pot, taking care that the specimens were completely immersed in the liquid.
  • test pieces were taken out and rinsed under running distilled water. Thereafter, the test pieces were rinsed in the domestic dishwasher with a formulation consisting of 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g of citric acid again with the 55 ° C program to remove any deposits ,
  • the dry specimens were weighed. This was followed by the visual assessment of the test specimens. The surface of the test specimens was evaluated for line corrosion (glass scoring) and haze corrosion (areal haze).
  • Interim scores (e.g., L3-4) were also allowed on the match.
  • formulations according to the invention were also always superior to the corresponding comparative formulations in terms of the inhibition of glass corrosion.
  • Table 2 Immersion tests example Base mixture: [g] (A.1) [g] (B) [mg] (C) [mg] Weight loss champagne glass [mg] Weight loss shot glass [mg] Visual rating champagne glass Visual rating schnapps glass V-1 Base 2: 19.37 5.63 --- 210 112 L1-2, T2 L1-2, T2 V-2 Base 2: 19.37 5.63 20 (B.1) --- 170 95 L2, T2 L1-2, T2 3 Base 2: 19.37 5.63 20 (B.1) 30 (C.1) 113 62 L2-3, T2-3 L2-3, T2-3 V-4 Base 2: 19.37 5.63 20 (B.2) --- 163 90 L2, T2 L2, T2 5 Base 2: 19.37 5.63 20 (B.2) 30 (C.1) 109 57 L2-3, T2-3 L2, T2-3 V-6 Base 2: 19.37 5.63 20 (B.3) --- 158 84 L2, T2 L2, T2 7 Base 2: 19.37 5.63 20 (B.3) --- 158

Description

Die vorliegende Erfindung betrifft Formulierungen, enthaltend

  1. (A) insgesamt im Bereich von 1 bis 50 Gew.-% mindestens einer Verbindung, gewählt aus Aminocarboxylaten und Polyaminocarboxylaten sowie deren Salzen,
  2. (B) insgesamt im Bereich von 0,05 bis 0,4 Gew-% mindestens eines Salzes von Wismut, angegeben als Wismut bzw. Wismut-Ionen, und
  3. (C) insgesamt im Bereich von 0,05 bis 2 Gew.-% mindestens ein Homo- oder Copolymer von Ethylenimin,
bezogen jeweils auf Feststoffgehalt der betreffenden Formulierung.The present invention relates to formulations containing
  1. (A) in total in the range from 1 to 50% by weight of at least one compound selected from aminocarboxylates and polyaminocarboxylates and their salts,
  2. (B) in total in the range of 0.05 to 0.4% by weight of at least one salt of bismuth, indicated as bismuth or bismuth ions, and
  3. (C) in the range of 0.05 to 2% by weight of at least one homopolymer or copolymer of ethyleneimine,
in each case based on solids content of the relevant formulation.

Weiterhin betrifft die vorliegende Erfindung ein Verfahren zur Herstellung von erfindungsgemäßen Formulierungen und ihre Verwendung als oder zur Herstellung von Geschirrspülmitteln, insbesondere von Geschirrspülmitteln für das maschinelle Geschirrreinigen.Furthermore, the present invention relates to a process for the preparation of formulations according to the invention and their use as or for the production of dishwashing detergents, in particular dishwashing detergents for machine dishwashing.

Geschirrspülmittel haben vielerlei Anforderungen zu erfüllen. So haben sie das Geschirr gründlich zu reinigen, sie sollen im Abwasser keine schädlichen oder potenziell schädlichen Substanzen aufweisen, sie sollen das Ablaufen und Trocknen des Wassers vom Geschirr gestatten, und sie sollen beim Betrieb der Spülmaschine nicht zu Problemen führen. Schließlich sollen sie nicht zu ästhetisch unerwünschten Folgen am zu reinigenden Gut führen. Besonders ist in diesem Zusammenhang die Glaskorrosion zu nennen.Dishwashing detergents have many requirements to fulfill. So they have to clean the dishes thoroughly, they should have no harmful or potentially harmful substances in the wastewater, they should allow the draining and drying of the water from the dishes, and they should not cause problems when operating the dishwasher. Finally, they should not lead to aesthetically undesirable consequences on the good to be cleaned. Especially in this context is the glass corrosion.

Glaskorrosion kommt nicht nur durch mechanische Effekte zustande, beispielsweise durch Aneinanderreiben von Gläsern oder mechanischen Kontakt der Gläser mit Teilen der Spülmaschine, sondern wird hauptsächlich durch chemische Einflüsse gefördert. Beispielsweise können bestimmte Ionen durch wiederholtes maschinelles Reinigen aus dem Glas gelöst werden, was die optischen und somit die ästhetischen Eigenschaften nachteilig verändert.Glass corrosion is caused not only by mechanical effects, for example by rubbing glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences. For example, certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.

Bei der Glaskorrosion beobachtet man mehrere Effekte. Zum einen kann man die Bildung von mikroskopisch feinen Rissen beobachten, die sich in Form von Linien bemerkbar machen. Zum anderen kann man in vielen Fällen eine generelle Eintrübung beobachten, beispielsweise eine Aufrauung, die das betreffende Glas unästhetisch aussehen lassen. Derartige Effekte werden insgesamt auch unterteilt in irisierende Verfärbung, Riefenbildung sowie flächen- und ringförmige Trübungen.Glass corrosion has several effects. On the one hand, one can observe the formation of microscopically fine cracks, which are noticeable in the form of lines. On the other hand, in many cases one can observe a general cloudiness, for example a roughening, which makes the glass in question look unaesthetic. Overall, such effects are also subdivided into iridescent discoloration, scoring and surface and annular opacities.

Aus US 5,981,456 und WO 99/05248 sind zahlreiche Geschirrspülmittel bekannt, denen man Zink-Salze oder Wismutsalze zusetzen kann, um Besteck vor dem Anlaufen oder der Korrosion zu schützen.Out US 5,981,456 and WO 99/05248 There are numerous dishwashing detergents which can be added with zinc salts or bismuth salts to protect cutlery from tarnishing or corrosion.

Aus WO 2002/64719 ist bekannt, dass man bestimmte Copolymere von ethylenisch ungesättigten Carbonsäuren mit beispielsweise Estern von ethylenisch ungesättigten Carbonsäuren in Geschirrspülmitteln einsetzen kann.Out WO 2002/64719 It is known that one can use certain copolymers of ethylenically unsaturated carboxylic acids with, for example, esters of ethylenically unsaturated carboxylic acids in dishwashing detergents.

In EP 1 721 962 A werden Formulierungen für das Geschirrspülen offenbart, die MGDA oder IDS und eine Wismutverbindung enthalten.In EP 1 721 962 A Dishwashing formulations containing MGDA or IDS and a bismuth compound are disclosed.

Aus WO 2010/020765 sind Geschirrspülmittel bekannt, die Polyethylenimin enthalten. Derartige Geschirrspülmittel können Phosphat enthalten oder Phosphat-frei sein. Es wird ihnen eine gute Inhibierung der Glaskorrosion zugeschrieben. Von Zink- und von Wismut-haltigen Geschirrspülmitteln wird abgeraten.Out WO 2010/020765 Dishwashing agents are known which contain polyethyleneimine. Such dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion. Zinc and bismuth-containing dishwashing detergents are not recommended.

Die Glaskorrosion, insbesondere die Linienkorrosion und die Trübung, wird aber in vielen Fällen noch nicht ausreichend verzögert oder verhindert.The glass corrosion, in particular the line corrosion and the turbidity, but is not sufficiently delayed or prevented in many cases.

Es bestand also die Aufgabe, Formulierungen bereit zu stellen, die als oder zur Herstellung von Geschirrspülmitteln geeignet sind und die die aus dem Stand der Technik bekannten Nachteile vermeiden und die Glaskorrosion inhibieren oder zumindest besonders gut verringern. Es bestand weiterhin die Aufgabe, ein Verfahren zur Herstellung von Formulierungen bereit zu stellen, die als oder zur Herstellung von Geschirrspülmitteln geeignet sind und die die aus dem Stand der Technik bekannten Nachteile vermeiden. Es bestand weiterhin die Aufgabe, Verwendungen von Formulierungen bereit zu stellen.It was therefore the object to provide formulations which are suitable as or for the production of dishwashing agents and which avoid the disadvantages known from the prior art and inhibit glass corrosion or at least reduce it particularly well. A further object was to provide a process for the preparation of formulations which are suitable as or for the production of dishwasher detergents and which avoid the disadvantages known from the prior art. It was also the task to provide uses of formulations.

Dementsprechend wurden die eingangs definierten Formulierungen gefunden, kurz auch erfindungsgemäße Formulierungen genannt.Accordingly, the formulations defined above were found, also called formulations according to the invention.

Erfindungsgemäße Formulierungen enthaltenContain formulations according to the invention

(A) insgesamt im Bereich von 1 bis 50 Ges.-% mindestens einer Verbindung, gewählt aus Aminocarboxylaten und Polyaminocarboxylaten, im Rahmen der vorliegenden Erfindung kurz auch Aminocarboxylat (A) bzw. Polyarrminocarboxylat (A) oder auch Verbindung (A) genannt, sowie deren Derivaten und vorzugsweise Salzen.(A) in total in the range of 1 to 50% by weight of at least one compound selected from aminocarboxylates and polyaminocarboxylates, in the context of the present invention also briefly aminocarboxylate (A) or polyarrminocarboxylate (A) or compound (A) called, and their derivatives and preferably salts.

Verbindung (A) kann als freie Säure oder vorzugsweise in partiell oder vollständig neutralisierter Form, also als Salz, vorliegen. Als Gegenionen kommen beispielsweise anorganische Kationen, beispielsweise Ammonium, Alkali oder Erdalkali in Frage, bevorzugt Mg2+, besonders bevorzugt Na+, K+, oder organische Kationen, bevorzugt mit einem oder mehreren organischen Resten substituiertes Ammonium, insbesondere Triethanolammonium, N,N-Diethanolammonium, N-Mono-C1-C4-alkyldiethanolammonium, beispielsweise N-Methyl-diethanolammonium oder N-n-Butyldiethanolammonium, und N,N-Di-C1-C4-alkylethanolammonium.Compound (A) may be in the form of a free acid or preferably in partially or completely neutralized form, ie as a salt. As counterions, for example inorganic cations, such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, more preferably Na +, K +, or organic cations, preferably substituted with one or more organic radicals ammonium, in particular triethanol ammonium, 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.

In einer Ausführungsform der vorliegenden Erfindung wählt man Verbindung (A) aus Derivaten von Aminocarboxylaten und Polyaminocarboxylaten, beispielsweise aus Methyl- oder Ethylestern.In one embodiment of the present invention, compound (A) is selected from derivatives of aminocarboxylates and polyaminocarboxylates, for example methyl or ethyl esters.

Unter Aminocarboxylaten (A) werden im Rahmen der vorliegenden Erfindung Nitrilotriessigsäure und solche organischen Verbindungen verstanden, die eine tertiäre Aminogruppe aufweisen, die eine oder zwei CH2-COOH-Gruppen aufweist, die - wie vorstehend erwähnt - partiell oder vollständig neutralisiert sein kann bzw. können. Unter Polyaminocarboxylaten (A) werden im Rahmen der vorliegenden Erfindung solche organischen Verbindungen verstanden, die mindestens zwei tertiäre Aminogruppen aufweisen, die unabhängig voneinander je eine oder zwei CH2-COOH-Gruppen aufweisen, die - wie vorstehend erwähnt - partiell oder vollständig neutralisiert sein kann bzw. können.In the context of the present invention, aminocarboxylates (A) are understood as meaning nitrilotriacetic acid and those organic compounds which have a tertiary amino group which has one or two CH 2 -COOH groups which, as mentioned above, can be partially or completely neutralized or can. In the context of the present invention, polyaminocarboxylates (A) are understood as meaning those organic compounds which have at least two tertiary amino groups which independently of one another have one or two CH 2 -COOH groups which, as mentioned above, can be partially or completely neutralized or can.

In einer anderen Ausführungsform der vorliegenden Erfindung wählt man Aminocarboxylate (A) aus solchen organischen Verbindungen, die eine sekundäre Aminogruppe aufweisen, die eine oder zwei CH(COOH)CH2-COOH-Gruppe(n) aufweist, die - wie vorstehend erwähnt - partiell oder vollständig neutralisiert sein kann bzw. können. In einer anderen Ausführungsform der vorliegenden Erfindung wählt man Polyaminocarboxylate (A) aus solchen organischen Verbindungen, die mindestens zwei sekundäre Aminogruppen aufweisen, die je eine CH(COOH)CH2-COOH-Gruppe aufweisen, die - wie vorstehend erwähnt - partiell oder vollständig neutralisiert sein können.In another embodiment of the present invention, aminocarboxylates (A) are selected from those organic compounds having a secondary amino group having one or two CH (COOH) CH 2 -COOH group (s) partially as mentioned above or can be completely neutralized. In another embodiment of the present invention, polyaminocarboxylates (A) are selected from those organic compounds having at least two secondary amino groups each containing a CH (COOH) CH 2 -COOH group which, as mentioned above, partially or completely neutralizes could be.

Bevorzugte Polyaminocarboxylate (A) sind gewählt aus 1,2-Diaminoethantetraessigsäure, Iminodisuccinat (IDS), Diethylentriaminpentaacetat (DTPA), Hydroxyethylendiamintriacetat (HEDTA), und ihre jeweiligen Salze, insbesonders bevorzugt die Alkalimetallsalze, insbesondrere die Natriumsalze.Preferred polyaminocarboxylates (A) are selected from 1,2-diaminoethanetetraacetic acid, iminodisuccinate (IDS), diethylenetriamine pentaacetate (DTPA), hydroxyethylenediaminetriacetate (HEDTA), and their respective salts, most preferably the alkali metal salts, especially the sodium salts.

Bevorzugte Aminocarboxylate (A) und Polyaminocarboxylate (A) sind Nitrilotriessigsäure und solche organischen Verbindungen, die eine Struktur auf Basis einer Aminosäure haben, deren Aminogruppe(n) eine oder zwei CH2-COOH-Gruppen aufweist bzw. aufweisen und tertiäre Aminogruppen sind. Dabei kann man Aminosäuren wählen aus L-Aminosäuren, R-Aminosäuren und Enantiomerengemischen von Aminosäuren, beispielsweise den Racematen.Preferred aminocarboxylates (A) and polyaminocarboxylates (A) are nitrilotriacetic acid and those organic compounds having an amino acid-based structure whose amino group (s) have one or two CH 2 -COOH groups and are tertiary amino groups. It is possible to select amino acids from L-amino acids, R-amino acids and mixtures of enantiomers of amino acids, for example the racemates.

In einer Ausführungsform der vorliegenden Erfindung wählt man Verbindung (A) aus Methylglycindiacetat (MGDA), Nitrilotriessigsäure und Glutaminsäurediacetat sowie deren Derivaten und vorzugsweise deren Salzen, insbesondere deren Natriumsalzen. Ganz besonders bevorzugt sind Methylglycindiacetat sowie das Trinatriumsalz von MGDA.In one embodiment of the present invention, compound (A) is selected from methylglycine diacetate (MGDA), nitrilotriacetic acid and glutamic acid diacetate and their derivatives and preferably their salts, in particular their sodium salts. Very particular preference is given to methylglycine diacetate and to the trisodium salt of MGDA.

Erfindungsgemäße Formulierungen enthalten insgesamt im Bereich von 0,05 bis 0,4 Gew.-% mindestens eines Salzes von Wismut (B). Salze von Wismut (B) kann man wählen aus wasserlöslichen und nicht wasserlöslichen Salzen von Wismut. Dabei werden im Rahmen der vorliegenden Erfindung solche Salze von Wismut (B) als nicht wasserlöslich bezeichnet, die in destilliertem Wasser bei 25°C eine Löslichkeit von 0,1 g/l oder weniger aufweisen. Salze von Wismut (B), die eine höhere Wasserlöslichkeit aufweisen, werden dementsprechend im Rahmen der vorliegenden Erfindung als wasserlösliche Salze von Wismut bezeichnet.Overall, formulations according to the invention contain in the range from 0.05 to 0.4% by weight of at least one salt of bismuth (B). Salts of bismuth (B) can be selected from water-soluble and non-water-soluble salts of bismuth. In the context of the present invention, such salts of bismuth (B) are said to be insoluble in water and are distilled in water Water at 25 ° C have a solubility of 0.1 g / l or less. Salts of bismuth (B), which have a higher water solubility, are accordingly referred to in the context of the present invention as water-soluble salts of bismuth.

In einer Ausführungsform der vorliegenden Erfindung wählt man Salz von Wismut (B) aus Wismutacetat, Wismutnitrat, Wismutsulfat, Wismuttriformiat ("Wismutformiat"), Wismutgallat und Wismuttrismethansulfonat, bevorzugt sind Wismutgallat und Wismuttrismethansulfonat.In one embodiment of the present invention, bismuth (B) salt is selected from bismuth acetate, bismuth nitrate, bismuth sulfate, bismuth tri-formate ("bismuth formate"), bismuth gallate and bismuth trismethanesulfonate, preferably bismuth gallate and bismuth trismethanesulfonate.

In einer anderen Ausführungsform der vorliegenden Erfindung wählt man Salz von Wismut (B) aus Bi2O3, Bi2O3·aq, BiO(OH). Bevorzugt ist BiO(OH).In another embodiment of the present invention, salt of bismuth (B) is selected from Bi 2 O 3 , Bi 2 O 3 · aq, BiO (OH). Preference is given to BiO (OH).

In einer Ausführungsform der vorliegenden Erfindung wählt man Salz von Wismut (B) aus Wismut-Oxiden mit einem mittleren Partikeldurchmesser (Gewichtsmittel) im Bereich von 10 nm bis 100 µm.In one embodiment of the present invention, salt of bismuth (B) is selected from bismuth oxides having an average particle diameter (weight average) in the range of 10 nm to 100 μm.

Das Kation in Salz von Wismut (B) kann komplexiert, beispielsweise mit Amoniak-Liganden oder mit Wasser-Liganden komplexiert, und insbesondere hydratisiert vorliegen. Zur Vereinfachung der Schreibweise werden im Rahmen der vorliegenden Erfindung Liganden in der Regel weggelassen, wenn es sich um Wasser-Liganden handelt.The cation in salt of bismuth (B) can be complexed, for example, complexed with ammonia ligands or with water ligands, and in particular be present hydrated. To simplify the notation, ligands are usually omitted in the context of the present invention, if they are water ligands.

Je nachdem, wie man den pH-Wert von erfindungsgemäßer Mischung einstellt, kann sich Salz von Wismut (B) umwandeln. So ist es beispielsweise möglich, dass man zur Herstellung von erfindungsgemäßer Formulierung Wismutacetat oder BiCl3 einsetzt, dieses sich aber bei einem pH-Wert von 8 oder 9 in wässriger Umgebung zu BiO(CH3COO) bzw. BiOCl, BiO(OH) oder Bi2O3·aq umwandelt, welches in nicht komplexierter oder in komplexierter Form vorliegen kann.Depending on how to adjust the pH of mixture according to the invention, salt of bismuth (B) can be converted. It is thus possible, for example, to use bismuth acetate or BiCl 3 for the preparation of the formulation according to the invention, but at a pH of 8 or 9 in an aqueous environment to form BiO (CH 3 COO) or BiOCl, BiO (OH) or Bi 2 O 3 · aq converts, which may be present in uncomplexed or complexed form.

Salz von Wismut (B) liegt in solchen erfindungsgemäßen Formulierungen, die bei Zimmertemperatur fest sind, vorzugsweise in Form von Partikeln vor, die beispielsweise einen mittleren Durchmesser (Zahlenmittel) im Bereich von 10 nm bis 100 µm, bevorzugt 100 nm bis 5 µm haben, bestimmt beispielsweise durch Röntgenstreuung.Salt of bismuth (B) is present in such formulations according to the invention which are solid at room temperature, preferably in the form of particles, for example having a mean diameter (number average) in the range of 10 nm to 100 μm, preferably 100 nm to 5 μm, determined, for example, by X-ray scattering.

Salz von Wismut (B) liegt in solchen erfindungsgemäßen Formulierungen, die bei Zimmertemperatur flüssig sind, in gelöster oder in fester oder in kolloidaler Form vor.Salt of bismuth (B) is present in such formulations according to the invention, which are liquid at room temperature, in dissolved or in solid or in colloidal form.

Erfindungsgemäße Formulierung enthält weiterhin (C) insgesamt im Bereich von 0,05 bis 2 Gew.-% mindestens ein Copolymer oder vorzugsweise ein Homopolymer von Ethylenimin, zusammen kurz auch Polyethylenimin (C) genannt.Formulation according to the invention furthermore contains (C) in the range from 0.05 to 2% by weight in total of at least one copolymer or preferably a homopolymer of ethyleneimine, together referred to in short as polyethyleneimine (C).

Unter Copolymeren des Ethylenimins sind im Rahmen der vorliegenden Erfindung auch Copolymerisate von Ethylenimin (Aziridin) mit einem oder mehreren höheren Homologen des Ethylenimins, wie Propylenimin (2-Methylaziridin), 1- oder 2-Butylenimin (2-Ethylaziridin bzw. 2,3-Dimethylaziridin), zu verstehen, beispielsweise mit 0,01 bis 75 mol-% an einem oder mehreren Homologen von Ethylenimin, bezogen auf den Anteil an Ethylenimin. Bevorzugt sind jedoch solche Copolymere, die nur Ethylenimin und im Bereich von 0,01 bis 5 mol-% Homologe des Ethylenimins einpolymerisiert enthalten, und insbesondere Homopolymerisate des Ethylenimins.For the purposes of the present invention, copolymers of ethyleneimine also include copolymers of ethyleneimine (aziridine) with one or more higher homologues of ethyleneimine, such as propyleneimine (2-methylaziridine), 1- or 2-butylenimine (2-ethylaziridine or Dimethylaziridine), for example, with 0.01 to 75 mol% of one or more Homologs of ethyleneimine, based on the proportion of ethyleneimine. However, preference is given to those copolymers which contain only ethyleneimine and in the range from 0.01 to 5 mol% of homologues of ethyleneimine in copolymerized form, and in particular homopolymers of ethyleneimine.

In einer Ausführungsform der vorliegenden Erfindung wählt man Copolymere des Ethylenimins (C) aus Pfropfcopolymerisaten des Ethylenimins (C). Derartige Pfropfcopolymerisate werden imIn one embodiment of the present invention, copolymers of ethyleneimine (C) are selected from graft copolymers of ethyleneimine (C). Such graft copolymers are in

In einer Ausführungsform der vorliegenden Erfindung wählt man Ethylenimin-Pfropfcopolymere (C) aus solchen Polymerisaten, die durch Pfropfen von Polyamidoaminen mit Ethylenimin erhältlich sind. Vorzugsweise sind Ethylenimin-Pfropfcopolymere (C) aus 10 bis 90 Gew.-% Polyamidoamin als Pfropfgrundlage und 90 bis 10 Gew.-% Ethylenimin als Pfropfauflage aufgebaut, jeweils bezogen auf Ethylenimin-Pfropfcopolymer (C).In one embodiment of the present invention, ethyleneimine graft copolymers (C) are selected from those polymers obtainable by grafting polyamidoamines with ethyleneimine. Preferably, ethyleneimine graft copolymers (C) are composed of 10 to 90% by weight of polyamidoamine as grafting base and 90 to 10% by weight of ethyleneimine as grafting support, each based on ethyleneimine graft copolymer (C).

Polyamidoamine sind beispielsweise erhältlich durch Kondensation von Polyalkylenpolyaminen in Reinform, als Gemisch untereinander oder im Gemisch mit Diaminen.Polyamidoamines are obtainable for example by condensation of polyalkylenepolyamines in pure form, as a mixture with one another or in a mixture with diamines.

Unter Polyalkylenpolyaminen werden im Rahmen der vorliegenden Erfindung solche Verbindungen verstanden, die mindestens 3 basische Stickstoffatome im Molekül enthalten, zum Beispiel Diethylentriamin, Dipropylentriamin, Triethylentetramin, Tripropylentetramin, Tetraethylenpentamin, Pentaethylenhexamin, N-(2-Aminoethyl)-1,3-propandiamin und N,N'-Bis(3-aminopropyl)ethylendiamin.In the context of the present invention, polyalkylenepolyamines are understood as meaning compounds which contain at least 3 basic nitrogen atoms in the molecule, for example diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N- (2-aminoethyl) -1,3-propanediamine and N , N'-bis (3-aminopropyl) ethylenediamine.

Geeignete Diamine sind beispielsweise 1,2-Diaminoethan, 1,3-Diaminopropan, 1,4-Diaminobutan, 1,6-Diaminohexan, 1,8-Diaminooctan, Isophorondiamin, 4,4'-Diaminodiphenylmethan, 1,4-Bis-(3-aminopropyl)piperazin, 4,9-Dioxadodecan-1,12-diamin, 4,7,10-Trioxatridecan-1,13-diamin und α,ω-Diaminoverbindungen von Polyalkylenoxiden.Examples of suitable diamines are 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, isophoronediamine, 4,4'-diaminodiphenylmethane, 1,4-bis ( 3-aminopropyl) piperazine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine and α, ω-diamino compounds of polyalkylene oxides.

In einer anderen Ausführungsform der vorliegenden Erfindung wählt man Ethylenimin-Pfropfcopolymere (C) aus solchen Polymerisaten, die man durch Pfropfen von Polyvinylaminen als Pfropfgrundlage mit Ethylenimin oder Oligomeren des Ethylenimins, beispielsweise Dimerren oder Trimeren des Ethylenimins, herstellen kann. Vorzugsweise sind Ethylenimin-Pfropfcopolymere (C) aus 10 bis 90 Gew.-% Polyvinylamin als Pfropfgrundlage und 90 bis 10 Gew.-% Ethylenimin als Pfropfauflage aufgebaut, jeweils bezogen auf Ethylenimin-Pfropfcopolymer (C).In another embodiment of the present invention, ethyleneimine graft copolymers (C) are selected from those polymers which can be prepared by grafting polyvinylamines as a grafting base with ethyleneimine or oligomers of ethyleneimine, for example dimerren or trimers of ethyleneimine. Preferably, ethyleneimine graft copolymers (C) are composed of 10 to 90% by weight of polyvinylamine as grafting base and 90 to 10% by weight of ethyleneimine as grafting support, in each case based on ethyleneimine graft copolymer (C).

Vorzugsweise wählt man als Komponente von erfindungsgemäßer Formulierung jedoch mindestens ein Polyethylenimin (C) in Form eines Homopolymers, vorzugsweise unvernetzt.Preferably, however, at least one polyethyleneimine (C) in the form of a homopolymer, preferably uncrosslinked, is chosen as the component of the formulation according to the invention.

Gemäß einer besonderen Ausführungsform der Erfindung weist Polyethylenimin (C) ein mittleres Molekulargewicht Mn von 500 g/mol bis 125.000 g/mol, bevorzugt von 750 g/mol bis 100.000 g/mol auf.According to a particular embodiment of the invention, polyethyleneimine (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 einer Ausführungsform der vorliegenden Erfindung weist Polyethylenimin (C) ein mittleres Molekulargewicht Mw im Bereich von 500 bis 1.000.000 g/mol auf, bevorzugt im Bereich von 600 bis 75.000 g/mol, besonders bevorzugt im Bereich von 800 bis 25.000 g/mol, bestimmbar beispielsweise durch Gelpermeationschromatographie (GPC).In one embodiment of the present invention, polyethyleneimine (C) has an average molecular weight M w 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, determinable for example by gel permeation chromatography (GPC).

In einer Ausführungsform der vorliegenden Erfindung wählt man Polyethylenimine (C) aus hochverzweigten Polyethyleniminen. Hochverzweigte Polyethylenimine (C) werden durch ihrenIn one embodiment of the present invention, polyethyleneimines (C) are selected from highly branched polyethyleneimines. Highly branched polyethyleneimines (C) are characterized by their

In einer Ausführungsform der vorliegenden Erfindung wählt man Polyethylenimine (C) aus hochverzweigten Polyethyleniminen. Hoch verzweigte Polyethylenimine (C) werden durch ihren hohen Verzweigungsgrad (Degree of Branching, DB) charakterisiert. Der Verzweigungsgrad lässt sich beispielsweise durch 13C-NMR-Spektroskopie, vorzugsweise in D2O, bestimmen und ist wie folgt definiert: DB = D + T / D + T + L

Figure imgb0001
mit D (dendritisch) entsprechend dem Anteil tertiärer Aminogruppen, L (linear) entsprechend dem Anteil sekundärer Aminogruppen und T (terminal) entsprechend dem Anteil primärer Aminogruppen.In one embodiment of the present invention, polyethyleneimines (C) are selected from highly branched polyethyleneimines. Highly branched polyethylenimines (C) 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
Figure imgb0001
 with D (dendritic) corresponding to the proportion of tertiary amino groups, L (linear) corresponding to the proportion of secondary amino groups and T (terminal) corresponding to the proportion of primary amino groups.

Als hochverzweigte Polyethylenimine (C) gelten im Rahmen der vorliegen Erfindung Polyethylenimine (C) mit DB im Bereich von 0,1 bis 0,95, bevorzugt 0,25 bis 0,90 besonders bevorzugt im Bereich von 0,30 bis 0,80 % und ganz besonders bevorzugt mindestens 0,5.Polyethyleneimines (C) having DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90 and more preferably in the range from 0.30 to 0.80%, are considered highly branched polyethylenimines (C) within the scope of the present invention. and most preferably at least 0.5.

Als dendrimere Polyethylenimine (C) gelten im Rahmen der vorliegen Erfindung Polyethylenimine (C) mit einem strukturell und molekular einheitlichen Aufbau.In the context of the present invention, polyethylene dendrimers (C) which are dendritic polyethylenimines (C) are understood as meaning polyethylenimines (C) having a structurally and molecularly uniform structure.

In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei Polyethylenimin (C) um hochverzweigte Polyethylenimine (Homopolymere) mit einem mittleren Molekulargewicht Mw im Bereich von 600 bis 75.000 g/mol, bevorzugt im Bereich von 800 bis 25.000 g/mol.In one embodiment of the present invention, polyethylenimine (C) is highly branched polyethyleneimines (homopolymers) having an average molecular weight M w in the range from 600 to 75,000 g / mol, preferably in the range from 800 to 25,000 g / mol.

Gemäß einer besonderen Ausführungsform der Erfindung handelt es sich bei Polyethylenimin (C) um hochverzweigte Polyethylenimine (Homopolymere) mit einem mittleren Molekulargewicht Mn von 500 g/mol bis 125.000 g/mol, bevorzugt von 750 g/mol bis 100.000 g/mol, das aus Dendrimeren gewählt wird.According to a particular embodiment of the invention, polyethylenimine (C) is highly branched polyethyleneimines (homopolymers) 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 is selected from dendrimers.

Erfindungsgemäße Formulierungen enthaltenContain formulations according to the invention

insgesamt im Bereich von 1 bis 50 Gew.-% Verbindung (A), bevorzugt 10 bis 25 Gew.-%, insgesamt im Bereich von 0,05 bis 0,4 Gew.-% Salz von Wismut (B), bevorzugt 0,1 bis 0,2 Gew.-%, und
insgesamt 0,05 bis 2 Gew.-% Homo- oder Copolymer von Ethylenimin (C), bevorzugt 0,1 bis 0,5 Gew.-%,
bezogen jeweils auf Feststoffgehalt der betreffenden Formulierung.in total in the range from 1 to 50% by weight of compound (A), preferably from 10 to 25% by weight, in total in the range from 0.05 to 0.4% by weight of bismuth (B) salt, preferably 0, 1 to 0.2 wt .-%, and
a total of from 0.05 to 2% by weight of homopolymer or copolymer of ethyleneimine (C), preferably from 0.1 to 0.5% by weight,
in each case based on solids content of the relevant formulation.

Dabei wird der Anteil Salz von Wismut als Wismut bzw. Wismut-Ionen angegeben. Dadurch kann man den Anteil des Gegenions herausrechnen. tur flüssig. In einer Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung ein Granulat, eine Flüssigzubereitung oder ein Gel.The proportion of salt of bismuth is given as bismuth or bismuth ions. Thus one can calculate out the portion of the Gegenions. liquid. In one embodiment of the present invention, the formulation according to the invention is a granulate, a liquid preparation or a gel.

Ohne einer bestimmten Theorie den Vorzug geben zu wollen, ist es möglich, dass in erfindungsgemäßen Formulierungen Salz von Wismut (B) in durch Polyethylenimin (C) komplexierter Form vorliegen kann.Without wishing to give preference to any particular theory, it is possible that salts of bismuth (B) may be present in formulations of the invention complexed by polyethylenimine (C).

In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäße Formulierung 0,1 bis 10 Gew.-% Wasser, bezogen auf die Summe aller Feststoffe der betreffenden Formulierung.In one embodiment of the present invention, the formulation according to the invention contains from 0.1 to 10% by weight of water, based on the sum of all solids of the relevant formulation.

In einer Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung frei von Phosphaten und Polyphosphaten, wobei Hydrogenphosphate mit subsumiert sind, beispielsweise frei von Trinatriumphosphat, Pentanatriumtripolyphosphat und Hexanatriummetaphosphat. Unter "frei von" soll im Zusammenhang mit Phosphaten und Polyphosphaten im Rahmen der vorliegenden Erfindung verstanden werden, dass der Gehalt an Phosphat und Polyphosphat in Summe im Bereich von 10 ppm bis 0,2 Gew.-% liegt, bestimmt durch Gravimetrie.In one embodiment of the present invention, formulation according to the invention is free of phosphates and polyphosphates, wherein hydrogen phosphates are subsumed, for example, free of trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate. The term "free from" in connection with phosphates and polyphosphates in the context of the present invention should be understood to mean that the total content of phosphate and polyphosphate ranges from 10 ppm to 0.2% by weight, determined by gravimetry.

In einer Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung frei von solchen Schwermetallverbindungen, die nicht als Bleichkatalysatoren wirken, insbesondere von Verbindungen des Eisens und des Zinks. Unter "frei von" soll im Zusammenhang mit Schwermetallverbindungen im Rahmen der vorliegenden Erfindung verstanden werden, dass der Gehalt an Schwermetallverbindungen, die nicht als Bleichkatalysatoren wirken, in Summe im Bereich von 0 bis 100 ppm liegt, bevorzugt 1 bis 30 ppm, bestimmt nach der Leach-Methode.In one embodiment of the present invention, the formulation of the present invention is free of those heavy metal compounds which do not function as bleach catalysts, especially compounds of iron and zinc. In the context of the present invention, "free from" is to be understood in connection with heavy metal compounds as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in the range from 0 to 100 ppm, preferably from 1 to 30 ppm, determined according to Leach method.

Als "Schwermetalle" gelten im Rahmen der vorliegenden Erfindung alle Metalle mit einer spezifischen Dichte von mindestens 6 g/cm3, aber nicht Wismut. Insbesondere gelten als Schwermetalle Edelmetalle sowie Zink, Eisen, Kupfer, Blei, Zinn, Nickel, Cadmium und Chrom.In the context of the present invention, "heavy metals" are all metals having a specific density of at least 6 g / cm 3 , but not bismuth. In particular, the heavy metals are precious metals and zinc, iron, copper, lead, tin, nickel, cadmium and chromium.

Vorzugsweise enthält erfindungsgemäße Formulierung keine messbaren Anteile an Zinkverbindungen, also beispielsweise weniger als 1 ppm.Preferably, formulation of the invention contains no measurable levels of zinc compounds, that is, for example, less than 1 ppm.

In einer Ausführungsform der vorliegenden Erfindung kann erfindungsgemäße Formulierung weitere Inhaltsstoffe (D) aufweisen, beispielsweise ein oder mehrere Tenside, ein oder mehrere Enzyme, einen oder mehrere Builder, insbesondere Phosphor-freie Builder, einen oder mehrere Cobuilder, einen oder mehrere Alkaliträger, ein oder mehrere Bleichmittel, einen oder mehrere Bleichkatalysatoren, einen oder mehrere Bleichaktivatoren, einen oder mehrere Bleichmittelstabilisatoren, einen oder mehrere Entschäumer, einen oder mehrere Korrosionsinhibitoren, einen oder mehrere Gerüststoffe, Puffer, Farbstoffe, einen oder mehrere Duftstoffe, ein oder mehrere organische Lösungsmittel, ein oder mehrere Tablettierhilfsmittel, ein oder mehrere Disintegrationsmittel, einen oder mehrere Verdicker, oder einen oder mehrere Löslichkeitsvermittler.In one embodiment of the present invention, formulation according to the invention may comprise further ingredients (D), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more a plurality of bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more perfumes, one or more organic solvents, one or more several tableting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizing agents.

Beispiele für Tenside sind insbesondere nicht-ionische Tenside sowie Mischungen von anionischen oder zwitterionischen Tensiden mit nicht-ionischen Tensiden. Bevorzugte nicht-ionische Tenside sind alkoxylierte Alkohole und alkoxylierte Fettalkohole, Di- und Multiblockcopolymerisate von Ethylenoxid und Propylenoxid und Umsetzungsprodukte von Sorbitan mit Ethylenoxid oder Propylenoxid, Alkylglycoside und sogenannte Aminoxide.Examples of surfactants are, in particular, nonionic surfactants and mixtures of anionic or zwitterionic surfactants with nonionic surfactants. Preferred nonionic surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.

Bevorzugte Beispiele für alkoxylierte Alkohole und alkoxylierte Fettalkohole sind beispielsweise Verbindungen der allgemeinen Formel (I)

Figure imgb0002
in der die Variablen wie folgt definiert sind:

  • R1 gewählt aus linearem C1-C10-Alkyl, bevorzugt Ethyl und besonders bevorzugt Methyl,
  • R2 gewählt aus C8-C22-Alkyl, beispielsweise n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33 oder n-C18H37,
  • R3 gewählt aus C1-C10-Alkyl, Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl oder iso-Decyl,
  • m und n liegen im Bereich von null bis 300, wobei die Summe von n und m mindestens eins beträgt. Bevorzugt ist m im Bereich von 1 bis 100 und n im Bereich von 0 bis 30.
Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I)
Figure imgb0002
 where the variables are defined as follows:
  • R 1 selected from linear C 1 -C 10 -alkyl, preferably ethyl and particularly preferably methyl,
  • R 2 is selected from C 8 -C 22 -alkyl, for example nC 8 H 17 , nC 10 H 21 , nC 12 H 25 , nC 14 H 29 , nC 16 H 33 or nC 18 H 37 ,
  • R 3 is selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- Decyl or iso-decyl,
  • m and n are in the range of zero to 300, where the sum of n and m is at least one. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

Dabei kann es sich bei Verbindungen der allgemeinen Formel (I) um Blockcopolymere oder statistische Copolymere handeln, bevorzugt sind Blockcopolymere.Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.

Andere bevorzugte Beispiele für alkoxylierte Alkohole und alkoxylierte Fettalkohole sind beispielsweise Verbindungen der allgemeinen Formel (II)

Figure imgb0003
in der die Variablen wie folgt definiert sind:

R5
gleich oder verschieden und gewählt aus linearem C1-C4-Alkyl, bevorzugt jeweils gleich und Ethyl und besonders bevorzugt Methyl,
R4
gewählt aus C6-C20-Alkyl, insbesondere n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33, n-C18H37.
a
eine Zahl im Bereich von 1 bis 6,
b
ist eine Zahl im Bereich von 4 bis 20,
d
ist eine Zahl im Bereich von 4 bis 25.
Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II)
Figure imgb0003
 where the variables are defined as follows:
R 5
identical or different and selected from linear C 1 -C 4 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,
R 4
selected from C 6 -C 20 -alkyl, in particular 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
a number in the range of 1 to 6,
b
is a number in the range of 4 to 20,
d
is a number in the range of 4 to 25.

Dabei kann es sich bei Verbindungen der allgemeinen Formel (II) um Blockcopolymere oder statistische Copolymere handeln, bevorzugt sind Blockcopolymere.In the case of compounds of the general formula (II), these may be block copolymers or random copolymers, preference being given to block copolymers.

Weitere geeignete nicht-ionische Tenside sind gewählt aus Di- und Multiblockcopolymeren, aufgebaut aus Ethylenoxid und Propylenoxid. Weitere geeignete nicht-ionische Tenside sind gewählt aus ethoxylierten oder propoxylierten Sorbitanestern. Ebenfalls eignen sich Aminoxide oder Alkylglycoside. Eine Übersicht geeigneter weiterer nichtionischer Tenside findet man in EP-A 0 851 023 und in DE-A 198 19 187 .Other suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Also suitable are amine oxides or alkyl glycosides. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187 ,

Es können auch Gemische mehrerer verschiedener nicht-ionischer Tenside enthalten sein.It may also contain mixtures of several different nonionic surfactants.

Beispiele für anionische Tenside sind C8-C20-Alkylsulfate, C8-C20-Alkylsulfonate und C8-C20-Alkylethersulfate mit einer bis 6 Ethylenoxideinheiten pro Molekül.Examples of anionic surfactants are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates having one to six ethylene oxide units per molecule.

In einer Ausführungsform der vorliegenden Erfindung kann erfindungsgemäße Formulierung im Bereich von 3 bis 20 Gew.-% Tensid enthalten.In one embodiment of the present invention, formulation of the invention may contain in the range of from 3 to 20% by weight of surfactant.

Erfindungsgemäße Formulierungen können ein oder mehrere Enzyme enthalten. Beispiele für Enzyme sind Lipasen, Hydrolasen, Amylasen, Proteasen, Cellulasen, Esterasen, Pectinasen, Lactasen und Peroxidasen.Formulations of the invention may contain one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.

Erfindungsgemäße Formulierungen können beispielsweise bis 5 Gew.-% Enzym enthalten, bevorzugt sind 0,1 bis 3 Gew.-%, jeweils bezogen auf gesamten Feststoffgehalt der erfindungsgemäßen Formulierung.Formulations according to the invention may contain, for example, up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, in each case based on the total solids content of the formulation according to the invention.

Erfindungsgemäße Formulierungen können einen oder mehrere Builder, insbesondere Phosphat-freie Builder, enthalten. Beispiele für geeignete Builder sind Silikate, insbesondere Natriumdisilikat und Natriummetasilikat, Zeolithe, Schichtsilikate, insbesondere solche der Formel α-Na2Si2O5, β-Na2Si2O5, und δ-Na2Si2O5, weiterhin Zitronensäure und ihre Alkalimetallsalze, Bernsteinsäure und ihre Alkalimetallsalze, Fettsäuresulfonate, α-Hydroxypropionsäure, Alkalimalonate, Fettsäuresulfonate, Alkyl- und Alkenyldisuccinate, Weinsäurediacetat, Weinsäuremonoacetat, oxidierte Stärke, und polymere Builder, beispielsweise Polycarboxylate und Polyasparaginsäure.Formulations according to the invention may contain one or more builders, in particular phosphate-free builders. Examples of suitable builders are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, especially those of the formula α-Na 2 Si 2 O 5 , β-Na 2 Si 2 O 5 , and δ-Na 2 Si 2 O 5 , furthermore citric acid and their alkali metal salts, succinic acid and its alkali metal salts, fatty acid sulfonates, α-hydroxypropionic acid, alkali malonates, Fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders such as polycarboxylates and polyaspartic acid.

In einer Ausführungsform der vorliegenden Erfindung wählt man Builder aus Polycarboxylaten, beispielsweise Alkalimetallsalze von (Meth)acrylsäurehomo- oder (Meth)acrylsäurecopolymeren.In one embodiment of the present invention, builders of polycarboxylates are selected, for example, alkali metal salts of (meth) acrylic acid homo- or (meth) acrylic acid copolymers.

Als Comonomere eignen sich monoethylenisch ungesättigte Dicarbonsäuren wie Maleinsäure, Fumarsäure, Maleinsäureanhydrid, Itaconsäure und Citraconsäure. Ein geeignetes Polymer ist insbesondere Polyacrylsäure, die bevorzugt ein mittleres Molekulargewicht Mw im Bereich von 2000 bis 40.000 g/mol aufweist, bevorzugt 2.000 bis 10.000 g/mol, insbesondere 3.000 bis 8.000 g/mol. Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure und/oder Fumarsäure.Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 2000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.

Es können auch Copolymere aus mindestens einem Monomeren aus der Gruppe bestehend aus monoethylenisch ungesättigten C3-C10-Mono- bzw. C4-C10-Dicarbonsäuren oder deren Anhydriden, wie Maleinsäure, Maleinsäureanhydrid, Acrylsäure, Methacrylsäure, Fumarsäure, Itaconsäure und Citraconsäure mit mindestens einem hydrophil oder hydrophob modifizierten Monomeren wie nachfolgend aufgezählt eingesetzt werden.It may also be copolymers of at least one monomer selected from the group consisting of 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 with at least one hydrophilic or hydrophobically modified monomers are used as listed below.

Geeignete hydrophobe Monomere sind beispielsweise Isobuten, Diisobuten, Buten, Penten, Hexen und Styrol, Olefine mit 10 oder mehr Kohlenstoffatomen oder deren Gemischen wie beispielsweise 1-Decen, 1-Dodecen, 1-Tetradecen, 1-Hexadecen, 1-Octadecen, 1-Eicosen, 1-Docosen, 1-Tetracosen und 1-Hexacosen, C22-α-Olefin, ein Gemisch aus C20-C24-α -Olefinen und Polyisobuten mit im Mittel 12 bis 100 C-Atomen pro Molekül.Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexadecene and 1-octadecene. eicosene, 1-docosene, 1-tetracosene, and 1-hexacosene, C 22 -α-olefin, a mixture of C 20 -C 24 -α-olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule.

Geeignete hydrophile Monomere sind Monomere mit Sulfonat- oder Phosphonatgruppen, sowie nichtionische Monomere mit Hydroxyfunktion oder Alkylenoxidguppen. Beispielsweise seien genannt: Allylalkohol, Isoprenol, Methoxypolyethylenglykol(meth)acrylat, Methoxypolypropylenglykol(meth)acrylat, Methoxypolybutylenglykol(meth)acrylat, Methoxypoly(propylenoxid-co-ethylenoxid)(meth)acrylat, Ethoxypolyethylenglykol(meth)acrylat, Ethoxypolypropylenglykol(meth)acrylat, Ethoxypolybutylenglykol(meth)acrylat und Ethoxypoly(propylenoxid-co-ethylenoxid)(meth)acrylat. Polyalkylenglykole können dabei 3 bis 50, insbesondere 5 bis 40 und vor allem 10 bis 30 Alkylenoxideinheiten pro Molekül enthalten.Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples which may be mentioned are: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate , Ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate. Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.

Besonders bevorzugte Sulfonsäuregruppen-haltige Monomere sind dabei 1-Acryl-amido-1-propansulfonsäure, 2-Acrylamido-2-propansulfonsäure, 2-Acrylamido-2-methylpropansulfonsäure, 2-Methacrylamido-2-methylpropansulfonsäure, 3-Meth-acrylamido-2-hydroxypropansulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Allyloxybenzolsulfonsäure, Methallyloxybenzolsulfonsäure, 2-Hydroxy-3-(2-propenyloxy)propansulfonsäure, 2-Methyl-2-propen-1-sulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 3-Sulfopropylacrylat, 2-Sulfoethylmethacrylat, 3-Sulfopropylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Salze der genannten Säuren, wie deren Natrium-, Kalium oder Ammoniumsalze.Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2 hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, Styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and salts of said acids, such as their sodium, potassium or ammonium salts.

Besonders bevorzugte Phosphonatgruppen-haltige Monomere sind die Vinylphosphonsäure und ihre Salze.Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.

Darüber hinaus können auch amphotere Polymere als Builder eingesetzt werden.In addition, amphoteric polymers can also be used as builders.

Erfindungsgemäße Formulierungen können beispielsweise im Bereich von insgesamt 10 bis 50 Gew.-%, bevorzugt bis 20 Gew.-% Builder enthalten.Formulations according to the invention may contain, for example, in the range from 10 to 50% by weight, preferably up to 20% by weight, of builder.

Erfindungsgemäße Formulierungen können einen oder mehrere Cobuilder enthalten.Formulations of the invention may contain one or more co-builders.

Beispiele für Cobuilder sind Phosphonate, beispielsweise Hydroxyalkanphosphonate und Aminoalkanphosphonate. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung als Cobuilder. Es wird vorzugsweise als Natriumsalz eingesetzt, wobei das Dinatriumsalz neutral und das Tetranatriumsalz alkalisch (pH-Wert 9) reagiert. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetra-methylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Sie werden vorzugsweise in Form der neutral reagierenden Natriumsalze, z.B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octa-Natriumsalz des DTPMP, eingesetzt.Examples of co-builders are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.

Erfindungsgemäße Formulierungen können einen oder mehrere Alkaliträger enthalten. Alkaliträger sorgen beispielsweise für den pH-Wert von mindestens 9, wenn ein alkalischer pH-Wert gewünscht wird. Geeignet sind beispielsweise Alkalimetallcarbonate, Alkalimetallhydrogencarbonate, Alkalimetallhydroxide und Alkalimetallmetasilikate. Bevorzugtes Alkalimetall ist jeweils Kalium, besonders bevorzugt ist Natrium.Formulations of the invention may contain one or more alkali carriers. Alkaline carriers, for example, provide the pH of at least 9 when an alkaline pH is desired. Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates. Preferred alkali metal is in each case potassium, particularly preferred is sodium.

Erfindungsgemäße Formulierungen können ein oder mehrere Bleichmittel enthalten, beispielsweise ein oder mehrere Sauerstoffbleichmittel oder ein oder mehrere Chlor-haltige Bleichmittel. Beispiele für geeignete Sauerstoffbleichmittel sind Natriumperborat, wasserfrei oder beispielsweise als Monohydrat oder als Tetrahydrat oder so genanntes Dihydrat, Natriumpercarbonat, wasserfrei oder beispielsweise als Monohydrat, Wasserstoffperoxid, Persulfate, organische Persäuren wie Peroxylaurinsäure, Peroxystearinsäure, Peroxy-α-Naphthoesäure, 1,12-Diperoxydodecandisäure, Perbenzoesäure, Peroxylaurinsäure, 1,9-Diperoxyazelainsäure, Diperoxyisophthalsäure, jeweils als freie Säure oder als alkalimetallsalz, insbesondere als Natriumsalz, weiterhin Sulfonylperoxysäuren und kationische Peroxysäuren.Formulations of the invention may contain one or more bleaches, for example, one or more oxygen bleaches, or one or more chlorine-containing bleaches. Examples of suitable oxygen bleaching agents are sodium perborate, anhydrous or, for example, monohydrate or tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-diperoxydodecanedioic acid , Perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as the free acid or as the alkali metal salt, in particular as the sodium salt, furthermore sulfonyl peroxyacids and cationic peroxyacids.

Erfindungsgemäße Formulierungen können beispielsweise im Bereich von 0,5 bis 15 Gew.-% Sauerstoffbleichmittel enthalten.For example, formulations according to the invention may contain in the range of 0.5 to 15% by weight of oxygen bleach.

Geeignete Chlor-haltige Bleichmittel sind beispielsweise 1,3-Dichloro-5,5-dimethylhydantoin, N-N-Chlorsulfamid, Chloramin T, Chloramin B, Natriumhypochlorit, Calciumhypochlorit, Magnesiumhypochlorit, Kaliumhypochlorit, Kaliumdichloroisocyanurat und Natriumdichloroisocyanurat.Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

Erfindungsgemäße Formulierungen können beispielsweise im Bereich von 3 bis 10 Gew.-% Chlor-haltiges Bleichmittel enthalten.For example, formulations according to the invention may contain in the range of from 3 to 10% by weight of chlorine-containing bleach.

Erfindungsgemäße Formulierungen können einen oder mehrere Bleichkatalysatoren enthalten. Bleichkatalysatoren kann man wählen aus bleichverstärkenden Übergangsmetallsalzen bzw. Übergangsmetallkomplexen wie beispielsweise Mangan-, Eisen-, Cobalt-, Ruthenium- oder Molybdän-Salenkomplexe oder Mangan-, Eisen-, Cobalt-, Ruthenium- oder Molybdäncarbonylkomplexe. Auch Mangan-, Eisen-, Kobalt-, Ruthenium-, Molybdän-, Titan-, Vanadium- und Kupfer-Komplexe mit stickstoffhaltigen Tripod-Liganden sowie Kobalt-, Eisen-, Kupfer- und Ruthenium-Aminkomplexe sind als Bleichkatalysatoren verwendbar.Formulations of the invention may contain one or more bleach catalysts. Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.

Erfindungsgemäße Formulierungen können einen oder mehrere Bleichaktivatoren, beispielsweise N-Methylmorpholinium-Acetonitril-Salze ("MMA-Salze"), TrimethylammoniumacetonitrilSalze, N-Acylimide wie beispielsweise N-Nonanoylsuccinimid" 1,5-Diacetyl-2,2-dioxohexahydro-1,3,5-triazin ("DADHT") oder Nitrilquats (Trimethylammoniumacetonitrilsalze) enthalten.Formulations of the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts"), trimethyl ammonium acetonitrile salts, N-acylimides such as N-nonanoyl succinimide, "1,5-diacetyl-2,2-dioxohexahydro-1,3 , 5-triazine ("DADHT") or nitrile quats (trimethylammonium acetonitrile salts).

Weitere Beispiele für geeignete Bleichaktivatoren sind Tetraacetylethylendiamin und Tetraacetylhexylendiamin.Further examples of suitable bleach activators are tetraacetylethylenediamine and tetraacetylhexylenediamine.

Erfindungsgemäße Formulierungen können einen oder mehrere Korrosionsinhibitoren enthalten. Darunter sind im vorliegenden Fall solche Verbindungen zu verstehen, die die Korrosion von Metall inhibieren. Beispiele für geeignete Korrosionsinhibitoren sind Triazole, insbesondere Benzotriazole, Bisbenzotriazole, Aminotriazole, Alkylaminotriazole, weiterhin Phenolderivate wie beispielsweise Hydrochinon, Brenzcatechin, Hydroxyhydrochinon, Gallussäure, Phloroglucin oder Pyrogallol.Formulations of the invention may contain one or more corrosion inhibitors. This is to be understood in the present case, such compounds that inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen insgesamt im Bereich von 0,1 bis 1,5 Gew.-% Korrosionsinhibitor.In one embodiment of the present invention, formulations according to the invention contain a total of in the range of 0.1 to 1.5 wt .-% corrosion inhibitor.

Erfindungsgemäße Formulierungen können einen oder mehrere Gerüststoffe enthalten, beispielsweise Natriumsulfat.Formulations of the invention may contain one or more builders, for example, sodium sulfate.

Erfindungsgemäße Formulierungen können einen oder mehrere Entschäumer enthalten, gewählt beispielsweise aus Silikonölen und Paraffinölen.Formulations of the invention may contain one or more defoamers selected, for example, from silicone oils and paraffin oils.

In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen insgesamt im Bereich von 0,05 bis 0,5 Gew.-% Entschäumer.In one embodiment of the present invention, formulations according to the invention contain in total in the range from 0.05 to 0.5% by weight defoamer.

In einer Ausführungsform der vorliegenden Erfindung können erfindungsgemäße Formulierungen eine oder mehrere Säuren enthalten, beispielsweise Methansulfonsäure.In one embodiment of the present invention, formulations according to the invention may contain one or more acids, for example methanesulfonic acid.

In einer Ausführungsform der vorliegenden Erfindung weisen erfindungsgemäße Formulierungen einen pH-Wert im Bereich von 5 bis 14 auf, bevorzugt 8 bis 13.In one embodiment of the present invention, formulations according to the invention have a pH in the range from 5 to 14, preferably 8 to 13.

Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßen Formulierungen zur maschinellen Reinigung von Geschirr und Küchenutensilien. Als Küchenutensilien sind im Rahmen der vorliegenden Erfindung beispielsweise Töpfe, Pfannen, Kasserollen zu nennen, weiterhin metallene Gegenstände wie beispielsweise Schaumlöffel, Bratenwender und Knoblauchpressen.Another object of the present invention is the use of formulations according to the invention for the automatic cleaning of dishes and kitchen utensils. As kitchen utensils in the context of the present invention, for example, pots, pans, casseroles to call, and metal objects such as, for example, skimmers, roasters and garlic presses.

Bevorzugt ist die die Verwendung von erfindungsgemäßen Formulierungen zur maschinellen Reinigung von Gegenständen, die mindestens eine Oberfläche aus Glas aufweisen, welches dekoriert oder nicht dekoriert sein kann. Dabei ist unter einer Oberfläche aus Glas im Rahmen der vorliegenden Erfindung zu verstehen, dass betreffender Gegenstand mindestens ein Stück aus Glas aufweist, das mit der Umgebungsluft in Berührung kommt und bei Gebrauch des Gegenstands verschmutzt werden kann. So kann es sich bei den betreffenden Gegenständen um solche handeln, die wie Trinkgläser oder Glasschüsseln im Wesentlichen gläsern sind. Es kann sich aber auch beispielsweise um Deckel handeln, die einzelne Komponenten aus einem anderen Material aufweisen, beispielsweise Topfdeckel mit Einfassung und Griff aus Metall.Preferred is the use of formulations according to the invention for machine cleaning of articles which have at least one surface of glass which may be decorated or not decorated. In the context of the present invention, a surface of glass is to be understood as meaning that the object in question has at least one piece of glass which comes into contact with the ambient air and can be contaminated when the object is used. Thus, the objects in question may be those which are essentially glassware such as drinking glasses or glass bowls. But it can also be, for example, cover that have individual components of a different material, such as pot lid with edging and metal handle.

Oberfläche aus Glas kann dekoriert, beispielsweise gefärbt oder bedruckt, oder nicht dekoriert sein.Glass surface may be decorated, for example colored or printed, or not decorated.

Unter dem Begriff "Glas" werden beliebige Gläser subsumiert, beispielsweise Bleiglas und insbesondere Kalknatronglas, Kristallglas und Borosilikatgläser.The term "glass" includes any glass, for example lead glass and in particular soda lime glass, crystal glass and borosilicate glasses.

Vorzugsweise handelt es sich bei maschineller Reinigung um ein Spülen mit einer Spülmaschine (englisch: automatic dishwashing").Machine cleaning is preferably dishwashing with a dishwasher (English: automatic dishwashing).

In einer Ausführungsform der vorliegenden Erfindung setzt man mindestens eine erfindungsgemäße Formulierung zur maschinellen Reinigung von Trinkgläsern, gläsernen Vasen und Glasgefäßen zum Kochen ein.In one embodiment of the present invention, at least one formulation according to the invention for automated cleaning of drinking glasses, glass vases and glass jars is used for cooking.

In einer Ausführungsform der vorliegenden Erfindung setzt man zum Reinigen Wasser mit einer Härte im Bereich von 1 bis 30 °dH, bevorzugt 2 bis 25 °dH ein, wobei unter deutscher Härte insbesondere die Calcium-Härte zu verstehen ist.In one embodiment of the present invention, water having a hardness in the range from 1 to 30 ° dH, preferably from 2 to 25 ° dH, is used for cleaning, German hardness being taken to mean in particular the calcium hardness.

Setzt man erfindungsgemäße Formulierungen zur maschinellen Reinigung ein, so beobachtet man auch bei wiederholter maschineller Reinigung von Gegenständen, die mindestens eine Oberfläche aus Glas aufweisen, nur sehr geringe Neigung zur Glaskorrosion, und zwar selbst dann, wenn man Gegenstände, die mindestens eine Oberfläche aus Glas aufweisen, zusammen mit stark verschmutztem Besteck oder Geschirr reinigt. Außerdem ist es deutlich weniger schädlich, erfindungsgemäße Formulierung einzusetzen, um Glas zusammen mit Gegenständen aus Metall zu reinigen, beispielsweise zusammen mit Töpfen, Pfannen oder Knoblauchpressen.If one uses formulations according to the invention for machine cleaning, it is observed even with repeated mechanical cleaning of objects which have at least one surface made of glass, only very slight tendency to glass corrosion, and even when you clean objects that have at least one surface of glass together with heavily soiled cutlery or dishes. In addition, it is much less harmful to use the formulation of the present invention to clean glass together with metal objects, such as pots, pans or garlic presses.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von erfindungsgemäßen Formulierungen, kurz auch erfindungsgemäßes Herstellungsverfahren genannt. Zur Durchführung des erfindungsgemäßen Herstellungsverfahrens kann man beispielsweise so vorgehen, dass man

  1. (A) mindestens eine Verbindung, gewählt aus Aminocarboxylaten und Polyaminocarboxylaten sowie deren Salzen und Derivaten,
  2. (B) mindestens ein Salz von Wismut,
  3. (C) mindestens ein Homo- oder Copolymer von Ethylenimin
und gegebenenfalls weitere Komponenten (D) in einem oder mehreren Schritten miteinander in Gegenwart von Wasser vermischt, beispielsweise verrührt, und anschließend das Wasser entfernt, und zwar vollständig oder zumindest teilweise.A further subject of the present invention is a process for the preparation of formulations according to the invention, in short also called production process according to the invention. For carrying out the preparation process according to the invention, it is possible, for example, to proceed in such a way that
  1. (A) at least one compound selected from aminocarboxylates and polyaminocarboxylates and their salts and derivatives,
  2. (B) at least one salt of bismuth,
  3. (C) at least one homo- or copolymer of ethyleneimine
and optionally other components (D) in one or more steps mixed together in the presence of water, for example, stirred, and then the water is removed, completely or at least partially.

Verbindung (A), Salz von Wismut (B) und Polyethylenimin (C) sind vorstehend definiert.Compound (A), salt of bismuth (B) and polyethyleneimine (C) are defined above.

In einer Ausführungsform der vorliegenden Erfindung kann man, bevor man das Wasser zumindest teilweise entfernt, mit einem oder mehreren weiteren Inhaltsstoffen (D) für erfindungsgemäße Formulierung vermischen, beispielsweise mit einem oder mehreren Tenside, einem oder mehreren Enzymen, einem oder mehreren Buildern, insbesondere Phosphor-freiem Builder, einem oder mehrere Cobuildern, einem oder mehreren Alkaliträgern, einem oder mehreren Bleichmitteln, einem oder mehreren Bleichkatalysatoren, einem oder mehreren Bleichaktivatoren, einem oder mehreren Bleichmittelstabilisatoren, einem oder mehreren Entschäumern, einem oder mehreren Korrosionsinhibitoren, einem oder mehreren Gerüststoffen, mit Puffer oder Farbstoff.In one embodiment of the present invention, before at least partially removing the water, one may mix with one or more further ingredients (D) for formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus free builder, one or more co-builders, one or more alkali carriers, one or more bleaches, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders Buffer or dye.

In einer Ausführungsform geht man so vor, dass man das Wasser ganz oder teilweise, beispielsweise bis zu einer Restfeuchte im Bereich von null bis 5 Gew.-% aus erfindungsgemäßer Formulierung entfernt, indem man es verdampft, insbesondere durch Sprühtrocknung, Sprühgranulierung oder Kompaktierung.In one embodiment, the water is removed completely or partially, for example to a residual moisture in the range from zero to 5% by weight, from the formulation according to the invention by evaporation, in particular by spray drying, spray granulation or compaction.

In einer Ausführungsform der vorliegenden Erfindung entfernt man das Wasser, ganz oder teilweise, bei einem Druck im Bereich von 0,3 bis 2 bar.In one embodiment of the present invention, the water is removed, in whole or in part, at a pressure in the range of 0.3 to 2 bar.

In einer Ausführungsform der vorliegenden Erfindung entfernt man das Wasser, ganz oder teilweise, bei Temperaturen im Bereich von 60 bis 220°C.In one embodiment of the present invention, the water is removed, in whole or in part, at temperatures in the range of 60 to 220 ° C.

Durch das erfindungsgemäße Herstellungsverfahren kann man erfindungsgemäße Formulierungen leicht erhalten.By means of the preparation process according to the invention, it is easy to obtain formulations according to the invention.

Die erfindungsgemäßen Reinigungsformulierungen können in flüssiger oder fester Form, ein- oder mehrphasig, als Tabletten oder in Form anderer Dosiereinheiten, verpackt oder unverpackt bereitgestellt werden. Der Wassergehalt von flüssigen Formulierungen kann variieren von 35 bis 90% Wasser.The cleaning formulations according to the invention can be provided in liquid or solid form, single- or multiphase, as tablets or in the form of other dosage units, packaged or unpackaged. The water content of liquid formulations can vary from 35 to 90% water.

Die Erfindung wird durch Arbeitsbeispiele verdeutlicht.The invention is illustrated by working examples.

Allgemeines: Es wurde darauf geachtet, dass man nach dem ersten Reinigen der Prüfkörper in der Haushaltsgeschirrspülmaschine bis nach dem Wiegen und visuellen Abmustern der Gläser die Prüfkörper nur mit sauberen Baumwollhandschuhen angefasst wurden, damit das Gewicht bzw. der visuelle Eindruck der Prüfkörper nicht verfälscht wurde.General: Care was taken that after the first cleaning of the specimens in the household dishwasher until after weighing and visual patterning of the glasses, the specimens were only touched with clean cotton gloves, so that the weight or the visual impression of the specimens was not falsified.

Im Rahmen der vorliegenden Erfindung bezeichnen % und ppm stets Gew.-% bzw. Gew.-ppm, wenn nicht ausdrücklich anders angegeben, und sind im Falle von erfindungsgemäßen Formulierungen auf dem Gesamt-Feststoffgehalt bezogen.In the context of the present invention,% and ppm always denote wt .-% and wt ppm, if not expressly stated otherwise, and in the case of formulations according to the invention based on the total solids content.

I. Herstellung erfindungsgemäßen FormulierungenI. Preparation of formulations according to the invention I.1 Herstellung von BasismischungenI.1 Preparation of basic mixtures

Zunächst wurden Basismischungen hergestellt, die die Einsatzstoffe gemäß Tabelle 1 enthielten. Tabelle 1: Basismischungen für Versuche mit erfindungsgemäßen Formulierungen und Vergleichsformulierungen Basis-1 Basis-2 Basis-3 Protease 2,5 2,5 2,5 Amylase 1 1 1 n-C18H37(OCH2CH2)9OH 5 5 5 Polyacrylsäure Mw 4.000 g/mol als Natriumsalz, vollständig neutralisiert 10 10 10 Natriumpercarbonat 10,5 10,5 10,5 TAED 4 4 4 Na2Si2O5 2 2 2 Na2CO3 19,5 19,5 19,5 Natriumcitrat Dihydrat 0 22,5 30 HEDP 0,5 0,5 0,5 Alle Mengenangaben in g. First, base mixtures were prepared containing the feedstocks according to Table 1. Table 1: Basic mixtures for experiments with formulations according to the invention and comparative formulations Base 1 Base 2 Base 3 protease 2.5 2.5 2.5 amylase 1 1 1 nC 18 H 37 (OCH 2 CH 2 ) 9 OH 5 5 5 Polyacrylic acid M w 4,000 g / mol as sodium salt, completely neutralized 10 10 10 sodium 10.5 10.5 10.5 TAED 4 4 4 Na 2 Si 2 O 5 2 2 2 Na 2 CO 3 19.5 19.5 19.5 Sodium citrate dihydrate 0 22.5 30 HEDP 0.5 0.5 0.5 All quantities in g.

Abkürzungen:Abbreviations:

  • MGDA: Methylglycindiessigsäure als TrinatriumsalzMGDA: methylglycine diacetic acid as trisodium salt
  • TAED: N,N,N',N'-TetraacetylethylendiaminTAED: N, N, N ', N'-tetraacetylethylenediamine
  • HEDP: Dinatriumsalz der Hydroxyethan-(1,1-diphosphonsäure)HEDP: disodium salt of hydroxyethane (1,1-diphosphonic acid)
I.2 Herstellung von erfindungsgemäßen FormulierungenI.2 Preparation of formulations according to the invention

In einem 100-ml-Becherglas legte man 20 ml destilliertes Wasser vor und gab nacheinander unter Rühren zu:

  • Salz von Wismut (B.1) oder (B.2) oder (B.3) oder (B.4) oder (B.5) gemäß Tabelle 2 Polyethylenimin (C.1), (C.2) oder (C.3) gemäß Tabelle 2
In a 100 ml beaker, 20 ml of distilled water were added and successively added with stirring:
  • Salt of bismuth (B.1) or (B.2) or (B.3) or (B.4) or (B.5) according to Table 2 polyethyleneimine (C.1), (C.2) or (C .3) according to Table 2

Man rührte 10 Minuten bei Zimmertemperatur. Anschließend gab man MGDA-Trinatriumsalz (A.1), gelöst in 30 ml Wasser, gemäß Tabelle 2 zu. Man erhielt eine klar durchsichtige Lösung. Danach gab man Basismischung gemäß Tabelle 2 zu, rührte erneut um und verdampfte das Wasser.
Man erhielt erfindungsgemäße Formulierungen, die man gemäß Tabelle 2 testete.The mixture was stirred for 10 minutes at room temperature. Then, MGDA trisodium salt (A.1) dissolved in 30 ml of water was added as shown in Table 2. A clear solution was obtained. Thereafter, base mixture according to Table 2 was added, stirred again and evaporated the water.
There were obtained formulations according to the invention, which were tested according to Table 2.

Zur Herstellung von Vergleichsformulierungen ging man analog vor, ließ jedoch das Salz von Wismiut (B) oder das Polyethylenimin (C) oder beides weg.To prepare comparative formulations, the procedure was analogous, but leaving out the salt of Wismiut (B) or the polyethyleneimine (C) or both.

Wenn man beim Immersionstest die entsprechenden Anteile Basismischung getrennt von wässriger Lösung von (A.1), (B) oder (C) dosierte, erhielt man die gleichen Ergebnisse, wie wenn man die getrocknete Formulierung mit gleichen Mengen an Wirkstoffen testete. Es kommt also nicht auf die Reihenfolge der Dosierung an.

  • (B.1) Wismutnitrat: Bi(NO3)3·5H2O
  • (B.2) Wismutsulfat Bi2(SO4)3
  • (B.3) Wismutformiat
  • (B.4) Wismuttrismethansulfonat
  • (B.5) Wismutgallat
Mengenangaben der Wismutsalze beziehen sich stets auf Wismut.
  • (C.1): Polyethylenimin-Homopolymer, Mw 800 g/mol, DB = 0,63
  • (C.2): Polyethylenimin-Homopolymer, Mw 5.000 g/mol, DB = 0,67
  • (C.3): Polyethylenimin-Homopolymer, Mw 25.000 g/mol, DB = 0,70
By dosing the corresponding proportions of the base mixture separately from the aqueous solution of (A.1), (B) or (C) during the immersion test, the same results were obtained as when the dried formulation was tested with equal amounts of active ingredients. So it does not depend on the order of the dosage.
  • (B.1) Bismuth nitrate: Bi (NO 3 ) 3 .5H 2 O
  • (B.2) bismuth sulfate Bi 2 (SO 4 ) 3
  • (B.3) bismuth formate
  • (B.4) bismuth trismethanesulfonate
  • (B.5) bismuth gallate
Quantities of bismuth salts always refer to bismuth.
  • (C.1): Polyethyleneimine homopolymer, Mw 800 g / mol, DB = 0.63
  • (C.2): Polyethyleneimine homopolymer, M w 5,000 g / mol, DB = 0.67
  • (C.3): Polyethyleneimine homopolymer, M w 25,000 g / mol, DB = 0.70

II. Verwendung von erfindungsgemäßen Formulierungen und Vergleichsformulierungen zum maschinellen Reinigen von GläsernII. Use of formulations according to the invention and comparative formulations for machine cleaning of glasses

Die Prüfung von erfindungsgemäßen Formulierungen und Vergleichsformulierungen erfolgte wie folgt.The testing of formulations according to the invention and comparative formulations was carried out as follows.

II.1 Prüfmethode ImmersionstestII.1 Test method Immersion test Geräte:Equipment:

Edelstahltopf (Volumen ca. 6 Liter) mit Deckel mit Loch für Kontaktthermometer Gitterbodeneinsatz mit Halterung für den Edelstahltopf
Magnetrührer mit Rührstäbchen, Kontaktthermometer, Gummistopfen mit LochStainless steel pot (volume approx. 6 liters) with lid with hole for contact thermometer Grid base insert with holder for the stainless steel pot
Magnetic stirrer with stirrer, contact thermometer, rubber stopper with hole

Versuchsbedingungen:Test conditions:

  • Temperatur: 75°CTemperature: 75 ° C
  • Zeit: 72 StundenTime: 72 hours
  • 5 Liter destilliertes Wasser oder Wasser mit definierter Wasserhärte ("Härtewasser")5 liters of distilled water or water with defined water hardness ("hardness water")

Als Prüfkörper setzte man je ein Sektglas und ein Schnapsglas der Fa. Libbey (NL), ein, Material: Kalk-Soda-Gläser.The test specimens were each a champagne glass and a shot glass from the company Libbey (NL), a, material: soda-lime glasses.

Versuchsdurchführung:Experimental procedure:

Zunächst spülte man zum Zwecke der Vorbehandlung die Prüfkörper in einer Haushaltsgeschirrspülmaschine (Bosch SGS5602) mit 1 g Tensid (n-C18H37(OCH2CH2)10OH) und 1 g Zitronensäure, um eventuelle Verunreinigungen zu entfernen. Man trocknete die Prüfkörper, bestimmte ihr Gewicht und fixierte sie auf dem Gitterbodeneinsatz.First, for the purpose of pretreatment, the test pieces were rinsed in a domestic dishwasher (Bosch SGS5602) with 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 1 g of citric acid to remove any impurities. The test pieces were dried, their weight determined and fixed on the grid floor insert.

Man füllte den Edelstahltopf mit 5,5 Liter Wasser und fügte 25 g der entsprechenden erfindungsgemäßen Formulierung gemäß Tabelle 3 hinzu, wobei Tabelle 3 die aktiven Komponenten (A.1), gegebenenfalls (B), gegebenenfalls (C) und Basismischung von erfindungsgemäßer Formulierung bzw. Vergleichsformulierung jeweils einzeln spezifiziert. Man rührte die so erhaltene Reinigerflotte mit Hilfe des Magnetrührers bei 550 Umdrehungen pro Minute. Man installierte das Kontaktthermometer und deckte den Edelstahltopf mit dem Deckel, damit während des Versuchs kein Wasser verdunsten konnte. Man erwärmte auf 75°C und setzte den Gitterbodeneinsatz mit den beiden Prüfkörpern in den Edelstahltopf ein, wobei man darauf achtete, dass die Prüfkörper völlig in die Flüssigkeit eintauchten.The stainless steel pot was filled with 5.5 liters of water and added 25 g of the corresponding formulation according to the invention according to Table 3, where Table 3 shows the active components (A.1), optionally (B), optionally (C) and base mixture of formulation according to the invention or Comparison formulation individually specified. The resulting cleaner liquor was stirred by means of the magnetic stirrer at 550 revolutions per minute. They installed the contact thermometer and covered the stainless steel pot with the lid, so that no water could evaporate during the experiment. It was heated to 75 ° C and put the grid bottom insert with the two specimens in the stainless steel pot, taking care that the specimens were completely immersed in the liquid.

Nach Beendigung des Versuchs wurden die Prüfkörper herausgenommen und unter fließendem destilliertem Wasser abgespült. Danach spülte man die Prüfkörper in der Haushaltsgeschirrspülmaschine mit einer Formulierung, bestehend aus 1 g Tensid (n-C18H37(OCH2CH2)10OH) und 20 g Zitronensäure, erneut mit dem 55°C-Programm, um eventuelle Ablagerungen zu entfernen.After completion of the experiment, the test pieces were taken out and rinsed under running distilled water. Thereafter, the test pieces were rinsed in the domestic dishwasher with a formulation consisting of 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g of citric acid again with the 55 ° C program to remove any deposits ,

Zur Beurteilung des gravimetrischen Abtrags wurden die trockenen Prüfkörper gewogen. Anschließend erfolgte die visuelle Beurteilung der Prüfkörper. Hierbei beurteilte man die Oberfläbodeneinsatz mit den beiden Prüfkörpern in den Edelstahltopf ein, wobei man darauf achtete, dass die Prüfkörper völlig in die Flüssigkeit eintauchten.To assess the gravimetric removal, the dry specimens were weighed. This was followed by the visual assessment of the test specimens. Here one judged the surface use with the two specimens in the stainless steel pot, taking care that the specimens were completely immersed in the liquid.

Nach Beendigung des Versuchs wurden die Prüfkörper herausgenommen und unter fließendem destilliertem Wasser abgespült. Danach spülte man die Prüfkörper in der Haushaltsgeschirrspülmaschine mit einer Formulierung, bestehend aus 1 g Tensid (n-C18H37(OCH2CH2)10OH) und 20 g Zitronensäure, erneut mit dem 55°C-Programm, um eventuelle Ablagerungen zu entfernen.After completion of the experiment, the test pieces were taken out and rinsed under running distilled water. Thereafter, the test pieces were rinsed in the domestic dishwasher with a formulation consisting of 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g of citric acid again with the 55 ° C program to remove any deposits ,

Zur Beurteilung des gravimetrischen Abtrags wurden die trockenen Prüfkörper gewogen. Anschließend erfolgte die visuelle Beurteilung der Prüfkörper. Hierbei beurteilte man die Oberfläche der Prüfkörper hinsichtlich Linienkorrosion (Glasriefen) und Trübungskorrosion (flächenartige Trübung).To assess the gravimetric removal, the dry specimens were weighed. This was followed by the visual assessment of the test specimens. The surface of the test specimens was evaluated for line corrosion (glass scoring) and haze corrosion (areal haze).

Die Bewertungen erfolgten nach folgendem Schema.The assessments were made according to the following scheme.

Linienkorrosion:Line corrosion:

  • L5: keine Linien zu erkennenL5: no lines to recognize
  • L4: in sehr wenigen Bereichen geringe Linienbildung, feine LinienkorrosionL4: in very few areas low line formation, fine line corrosion
  • L3: in einigen Bereichen LinienkorrosionL3: line corrosion in some areas
  • L2: in mehreren Bereichen LinienkorrosionL2: line corrosion in several areas
  • L1: Stark ausgeprägte LinienkorrosionL1: Strong line corrosion
Glastrübungglass opacity

  • T5: keine Trübung zu erkennenT5: no haze visible
  • T4: in sehr wenigen Bereichen geringe TrübungT4: low turbidity in very few areas
  • T3: in einigen Bereichen TrübungenT3: cloudiness in some areas
  • T2: in mehreren Bereichen TrübungenT2: turbidity in several areas
  • T1: Stark ausgeprägte Trübung über fast die ganze GlasoberflächeT1: markedly turbid over almost the entire glass surface

Bei der Abmusterung wurden auch Zwischennoten (z.B. L3-4) zugelassen.Interim scores (e.g., L3-4) were also allowed on the match.

Wenn man statt Wasser Härtewasser mit 2 ° dH für die Tests einsetzte, so waren erfindungsgemäße Formulierungen den entsprechenden Vergleichsformulierungen ebenfalls stets überlegen, was die Inhibierung der Glaskorrosion betrifft.If hardness water at 2 ° dH was used instead of water for the tests, formulations according to the invention were also always superior to the corresponding comparative formulations in terms of the inhibition of glass corrosion.

II.2 ErgebnisseII.2 Results

Die Ergebnisse sind in Tabelle 2 zusammengefasst. Tabelle 2: Immersionstests Beispiel Basismischung: [g] (A.1) [g] (B) [mg] (C) [mg] Gewichtsverlust Sektglas [mg] Gewichtsverlust Schnapsglas [mg] Visuelle Bewertung Sektglas Visuelle Bewertung Schnaps glas V-1 Basis-2: 19,37 5,63 --- --- 210 112 L1-2, T2 L1-2, T2 V-2 Basis-2: 19,37 5,63 20 (B.1) --- 170 95 L2, T2 L1-2, T2 3 Basis-2: 19,37 5,63 20 (B.1) 30 (C.1) 113 62 L2-3, T2-3 L2-3,T2- 3 V-4 Basis-2: 19,37 5,63 20 (B.2) --- 163 90 L2, T2 L2, T2 5 Basis-2: 19,37 5,63 20 (B.2) 30 (C.1) 109 57 L2-3, T2-3 L2,T2-3 V-6 Basis-2: 19,37 5,63 20 (B.3) --- 158 84 L2, T2 L2, T2 7 Basis-2: 19,37 5,63 20 (B.3) 30 (C.2) 101 53 L3, T2-3 L3, T2-3 V-8 Basis-1: 13,75 11,25 20 (B.4) --- 154 82 L2-3, T2 L2-3, T2 9 Basis-1: 13,75 11,25 20 (B.4) 30 (C.1) 97 48 L3-4, T3 L3-4, T3 10 Basis-1: 13,75 11,25 20 (B.4) 30 (C.2) 103 50 L3, T3 L3, T3 V-11 Basis-1: 13,75 11,25 20 (B.5) --- 138 65 L2-3, T2-3 L2, T2-3 12 Basis-1: 13,75 11,25 20 (B.5) 30 (C.1) 65 35 L3-4, T4-5 L4, T4-5 13 Basis-1: 13,75 11,25 20 (B.5) 30 (C.2) 77 42 L3-4, T4 L4, T4 V-14 Basis-3: 21,25 3,75 20 (B.5) --- 120 60 L2-3, T2-3 L2-3, T2-3 15 Basis-3: 21,25 3,75 20 (B.5) 30 (C.1) 57 29 L4, T4-5 L4, T4-5 16 Basis-3: 21,25 3,75 20 (B.5) 30 (C.2) 61 32 L4, T4-5 L4, T4-5 17 Basis-3: 21,25 3,75 20 (B.5) 30 (C.3) 68 36 L4, T4 L4, T4 18 Basis-3: 21,25 3,75 40 (B.5) 30 (C.1) 48 24 L5, T4-5 L5, T4-5 19 Basis-3: 21,25 3,75 40 (B.5) 40 (C.1) 46 23 L5, T4-5 L5, T4-5 The results are summarized in Table 2. Table 2: Immersion tests example Base mixture: [g] (A.1) [g] (B) [mg] (C) [mg] Weight loss champagne glass [mg] Weight loss shot glass [mg] Visual rating champagne glass Visual rating schnapps glass V-1 Base 2: 19.37 5.63 --- --- 210 112 L1-2, T2 L1-2, T2 V-2 Base 2: 19.37 5.63 20 (B.1) --- 170 95 L2, T2 L1-2, T2 3 Base 2: 19.37 5.63 20 (B.1) 30 (C.1) 113 62 L2-3, T2-3 L2-3, T2-3 V-4 Base 2: 19.37 5.63 20 (B.2) --- 163 90 L2, T2 L2, T2 5 Base 2: 19.37 5.63 20 (B.2) 30 (C.1) 109 57 L2-3, T2-3 L2, T2-3 V-6 Base 2: 19.37 5.63 20 (B.3) --- 158 84 L2, T2 L2, T2 7 Base 2: 19.37 5.63 20 (B.3) 30 (C.2) 101 53 L3, T2-3 L3, T2-3 V-8 Base 1: 13.75 11.25 20 (B.4) --- 154 82 L2-3, T2 L2-3, T2 9 Base 1: 13.75 11.25 20 (B.4) 30 (C.1) 97 48 L3-4, T3 L3-4, T3 10 Base 1: 13.75 11.25 20 (B.4) 30 (C.2) 103 50 L3, T3 L3, T3 V-11 Base 1: 13.75 11.25 20 (B.5) --- 138 65 L2-3, T2-3 L2, T2-3 12 Base 1: 13.75 11.25 20 (B.5) 30 (C.1) 65 35 L3-4, T4-5 L4, T4-5 13 Base 1: 13.75 11.25 20 (B.5) 30 (C.2) 77 42 L3-4, T4 L4, T4 V-14 Base 3: 21.25 3.75 20 (B.5) --- 120 60 L2-3, T2-3 L2-3, T2-3 15 Base 3: 21.25 3.75 20 (B.5) 30 (C.1) 57 29 L4, T4-5 L4, T4-5 16 Base 3: 21.25 3.75 20 (B.5) 30 (C.2) 61 32 L4, T4-5 L4, T4-5 17 Base 3: 21.25 3.75 20 (B.5) 30 (C.3) 68 36 L4, T4 L4, T4 18 Base 3: 21.25 3.75 40 (B.5) 30 (C.1) 48 24 L5, T4-5 L5, T4-5 19 Base 3: 21.25 3.75 40 (B.5) 40 (C.1) 46 23 L5, T4-5 L5, T4-5

Claims (13)

  1. A formulation comprising
    (A) in total in the range from 1 to 50% by weight of at least one compound selected from aminocarboxylates and polyaminocarboxylates,
    (B) in total in the range from 0.05 to 0.4% by weight of at least one salt of bismuth (Bi), stated as bismuth or bismuth ions,
    (C) in total in the range from 0.05 to 2% by weight of at least one homo- or copolymer of ethyleneimine,
    based in each case on the solids content of the respective formulation.
  2. The formulation according to claim 1, which is free from phosphates and polyphosphates.
  3. The formulation according to claim 1 or 2, wherein (C) is selected from homopolymers of ethyleneimine, linear or branched, and graft copolymers of ethyleneimine.
  4. The formulation according to any one of claims 1 to 3, wherein salt of bismuth (B) is selected from bismuth gallate and bismuth trismethanesulfonate.
  5. The formulation according to any one of claims 1 to 4, wherein compound (A) is selected from methylglycine diacetate (MGDA), nitrilotriacetic acid and glutamic acid diacetate, and salts thereof.
  6. The formulation according to any one of claims 1 to 5, which is solid at room temperature.
  7. The formulation according to any one of claims 1 to 6, which comprises water in the range from 0.1 to 10% by weight.
  8. The use of formulations according to any one of claims 1 to 7 for washing crockery, cutlery and kitchen utensils.
  9. The use of formulations according to any one of claims 1 to 7 for washing objects which have at least one surface made of glass, which can be decorated or undecorated.
  10. The use according to claim 8 or 9, wherein the washing is washing using a dishwasher.
  11. The use according to any one of claims 8 to 10, wherein at least one formulation according to any one of claims 1 to 7 is used for washing drinking glasses, glass vases and glass vessels for cooking.
  12. A process for the preparation of formulations according to any one of claims 1 to 7, wherein
    (A) at least one compound selected from aminocarboxylates and polyaminocarboxylates,
    (B) at least one salt of bismuth,
    (C) at least one homo- or copolymer of ethyleneimine
    and optionally further components are mixed in one or more steps with one another in the presence of water, and then the water is removed.
  13. The process according to claim 12, wherein the water is removed by spray-drying.
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