EP2768935A1 - Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation - Google Patents

Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation

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Publication number
EP2768935A1
EP2768935A1 EP12762614.1A EP12762614A EP2768935A1 EP 2768935 A1 EP2768935 A1 EP 2768935A1 EP 12762614 A EP12762614 A EP 12762614A EP 2768935 A1 EP2768935 A1 EP 2768935A1
Authority
EP
European Patent Office
Prior art keywords
formulation
alkali metal
formulations
acid
glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12762614.1A
Other languages
German (de)
English (en)
Other versions
EP2768935B1 (fr
Inventor
Stephan Hueffer
Alejandra Garcia Marcos
Markus Hartmann
Heike Weber
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BASF SE
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BASF SE
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Application filed by BASF SE filed Critical BASF SE
Priority to EP12762614.1A priority Critical patent/EP2768935B1/fr
Priority to PL12762614T priority patent/PL2768935T3/pl
Publication of EP2768935A1 publication Critical patent/EP2768935A1/fr
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy 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
    • C11D3/26—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
    • C11D3/16—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

Definitions

  • the present invention relates to formulations containing
  • 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 agents, in particular dishwasher detergents for automatic 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 juxtaposition of 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.
  • WO 2002/64719 discloses that it is possible to use certain copolymers of ethylenically unsaturated carboxylic acids with, for example, esters of ethylenically unsaturated carboxylic acids in dishwashing detergents.
  • dishwashing agents which contain polyethyleneimine.
  • dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion.
  • zinc and bismuth-containing dishes Dishwashing is 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.
  • formulations according to the invention Contain formulations according to the invention
  • (A) at least one compound selected from aminocarboxylates and polyaminocarboxylates, in the context of the present invention also briefly aminocarboxylate (A) or Polyaminocar- boxylate (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+, preferably Na +, K +, or organic cations, preferably with one or more organic radicals substitutability tes ammonium, particularly triethanolammonium, ⁇ , ⁇ Diethanolammonium, N-mono-C 1 -C 4 -alkyldiethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N, N-di-C 1 -C 4 -alkylethanolammonium.
  • inorganic cations such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, preferably Na +, K +, or organic cations, preferably with one or more organic radicals substitutability
  • compound (A) is selected from derivatives of aminocarboxylates and polyaminocarboxylates, for example from methyl or ethyl esters.
  • aminocarboxylates (A) are understood to mean 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, are partially or completely neutralized can 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 or partially substituted as mentioned above can be completely neutralized or can.
  • polyaminocarboxylates (A) are selected from those organic compounds having at least two secondary amino groups each having a CH (COOH) CH 2 COOH group which, as mentioned above, may be partially or completely neutralized can.
  • Preferred polyaminocarboxylates (A) are selected from 1,2-diaminoethanetetraacetic acid, tetraacetylmethylenediamine, tetraacetylhexylenediamine, iminodisuccinate (IDS), diethylenetriamine pentaacetate (DTPA), hydroxyethylenediaminetriacetate (HEDTA), and their respective salts, particularly preferably alkali metal salts, in particular 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-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.
  • the formulation according to the invention also contains
  • polyethyleneimine (B) at least one homopolymer of ethyleneimine, together referred to as polyethyleneimine (B) for short.
  • polyethyleneimine (B) has an average molecular weight M n of from 500 g / mol to 125,000 g / mol, preferably from 750 g / mol to 100,000 g / mol.
  • polyethyleneimine (B) has an average molecular weight M w in the range from 500 to 1,000,000 g / mol, preferably in the range from 600 to 75,000 g / mol, particularly preferably in the range from 800 to 25,000 g / mol, determinable for example by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • polyethyleneimines (B) are selected from highly branched polyethyleneimines.
  • Highly branched polyethylenimines (B) 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:
  • highly branched polyethyleneimines (B) are polyethyleneimines (B) with DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90, particularly preferably in the range from 0.30 to 0.80%. and most preferably at least 0.5.
  • polyethylene dendrimers (B) are polyethyleneimines (B) having a structurally and molecularly uniform structure.
  • polyethylenimine (B) 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 (B) 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.
  • Formulations according to the invention also contain sodium citrate (C).
  • the term sodium citrate comprises the mono- and preferably the disodium salt with.
  • Sodium citrate can be used as anhydrous salt or as a hydrate, for example as a dihydrate.
  • Formulations according to the invention also contain
  • (D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, in the context of the present invention also called “bleaching agent (D)".
  • Preferred bleaching agents (D) are selected from sodium perborate, anhydrous or, for example, as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, and sodium persulfate, where the term "persulfate" in each case the salt of peracid H2SO5 and the peroxodisulfate with
  • the alkali metal salts may in each case also be alkali metal hydrogencarbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulphate, but the dialkali metal salts are preferred in each case.
  • formulations according to the invention contain in total in the range from 1 to 50% by weight of compound (A), preferably 10 to 25% by weight, in total from 0.05 to 2% by weight of homopolymer of ethyleneimine (B) , preferably 0.1 to 0.5% by weight, 1 to 50% by weight of sodium citrate (C), preferably 5 to 30% by weight, determined as anhydrous sodium citrate,
  • bleaching agent (D) selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.
  • formulation according to the invention is solid at room temperature, for example a powder or a tablet.
  • formulation according to the invention is liquid at room temperature.
  • the formulation according to the invention is a granulate, a liquid preparation or a gel.
  • formulation according to the invention contains from 0.1 to 10% by weight of water, based on the sum of all solids of the formulation in question.
  • 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 Hexasatriummeta- phosphate.
  • free of is meant in connection with phosphates and polyphosphates in the
  • the total content of phosphate and polyphosphate is in the range from 10 ppm to 0.2% by weight, determined by gravimetry.
  • the formulation according to the invention is free from those heavy metal compounds which do not function as bleach catalysts, in particular compounds of iron and bismuth.
  • “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, determined by the Leach method.
  • heavy metals are all metals having a specific density of at least 6 g / cm 3.
  • heavy metals include noble metals and zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium formulation according to the invention no measurable levels of zinc and bismuth compounds, that is, for example, less than 1 ppm.
  • formulation according to the invention may comprise further ingredients (E), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more co-builders, one or more alkali carriers 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, buffers, dyes, one or more perfumes, one or more organic solvents , one or more tableting aids, one or more dineintegrating agents, one or more thickeners, or one or more solubilizers.
  • surfactants for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more co-builders, one or more alkali carriers 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
  • 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.
  • alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I) in which the variables are defined as follows: R 1 selected from linear C 1 -C 10 -alkyl, preferably ethyl and particularly preferably methyl,
  • R 2 selected from Cs-C22-alkyl, for example nC & Hn, n-doFi, n-Ci2H25, nC-uF s), n-Ci6H33 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.
  • 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, the sum of n and m being at least one.
  • m is in the range of 1 to 100 and n is in the range of 0 to 30.
  • Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
  • Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II) where the variables are defined as follows:
  • R 1 is 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 n-CsH-i, n-doF i, n-Ci 2 H 25, nC-uF s), n-Ci6H33, n-
  • a is a number ranging from 1 to 6
  • b is a number ranging from 4 to 20
  • c is a number ranging from 4 to 25.
  • Compounds of general formula (II) may be block or random copolymers , preferred are 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. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187.
  • 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 comprise, in addition to sodium citrate, one or more builders, in particular phosphate-free builders.
  • Suitable builders are silicates, especially sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the formula a-Na 2 Si 2 O, ⁇ -Na 2 Si 2 O, and 5-Na 2 Si 2 O, furthermore fatty acid sulfonates, ⁇ -hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, wine acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders such as polycarboxylates and polyaspartic acid.
  • builders of polycarboxylates for example, alkali metal salts of (meth) acrylic acid homo- or
  • 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.
  • copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C3-Cio-mono- or C4-Cio-dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid with at least one hydrophilic or hydrophobically modified monomers as enumerated 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 - Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C22- ⁇ -olefin, a mixture of C2o-C24- ⁇ -olefins and polyisobutene having an average of 12 to 100 carbon atoms per molecule.
  • 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 monomers containing sulfonic acid groups 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
  • 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 according to the invention may contain one or more co-builders.
  • cobuilders are phosphonates, for example hydroxyalkanephosphonates and aminoalkanephosphonates.
  • hydroxyalkane phosphonates the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • 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 if 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 according to the invention in addition to bleach (D), contain one or more chlorine-containing bleaches.
  • 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 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 according to the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide "1, 5-diacetyl-2,2-dioxohexahydro -1, 3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • MMA salts N-methylmorpholinium acetonitrile salts
  • DADHT 3,5-triazine
  • nitrile quats trimethylammonium acetonitrile salts
  • 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 phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid.
  • 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.
  • 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
  • optionally further components (E) are mixed with one another in one or more steps in the presence of water, for example by stirring, and the water is then removed completely or at least partially.
  • Compound (A), salt of bismuth (B) and polyethyleneimine (C) are defined above.
  • one or more further ingredients (E) for the formulation according to the invention for example with one or more surfactants, one or more enzymes, one or more builders, one or more co-builders, in particular phosphorus-free builder, 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 several builders, with buffer or dye.
  • surfactants for example with one or more surfactants, one or more enzymes, one or more builders, one or more co-builders, in particular phosphorus-free builder, 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 several builders, with buffer or dye.
  • the water is completely or partially removed, for example, to a residual moisture in the range from zero to 5% by weight, from 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 from 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.
  • base mixtures were prepared containing the feedstocks according to Table 1.
  • the starting materials were mixed dry.
  • MGDA methylglycine diacetic acid as trisodium salt
  • TAED ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacetylethylenediamine
  • HEDP disodium salt of hydroxyethane- (1, 1-diphosphonic acid
  • Washware 3 champagne glasses “GILDE”, 3 shot glasses, "INTERMEZZO"
  • the dishwashing agent used was in each case 25 g of formulation according to the invention or comparative formulation according to Table 2, where Table 2 shows the active components (A.1), in each case individually specified, and rinsing at a rinse-aid temperature of 55 ° C.
  • the water hardness was in each case in the range from zero to 2 ° dH each rinsed 100 rinse cycles, ie, the program was allowed to run 100 times and evaluated gravimetrically and visually after 100 rinse cycles.
  • the weight of the glasses was determined before the beginning of the first rinse cycle and after drying after the last rinse cycle.
  • the weight loss is the difference between the two values.
  • a visual evaluation of the washware was given after 100 cycles in a darkened chamber under light behind a pinhole using a grading scale from 1 (very poor) to 5 (very good). In each case grades for area corrosion / turbidity or line corrosion were determined.
  • thermometer Stainless steel pot (volume approx. 6 liters) with lid with hole for contact thermometer
  • hardness water 5 liters of distilled water or water with defined water hardness
  • 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 for the purpose of pretreatment, the test pieces in a domestic dishwashing machine (Bosch SGS5602) with a 1 g surfactant (n-Ci8H37 (OCH 2 CH 2) ioOH) and 20 g of citric acid, to remove any impurities.
  • a domestic dishwashing machine Bosch SGS5602
  • n-Ci8H37 OH 2 CH 2 ioOH
  • citric acid 20 g
  • the stainless steel pot was filled with 5.5 liters of water and added 25 g of formulation or comparison formulation according to the invention, wherein Table 3 shows the active components (A.1), optionally (B), optionally (C) and base mixture of formulation according to the invention or comparison formulation each individually specified.
  • the resulting cleaner liquor was stirred by means of the magnetic stirrer at 550 revolutions per minute. It installed the contact thermometer and covered the stainless steel pot with the lid, so that during the experiment no water could evaporate. 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. After completion of the experiment, the test pieces were taken out and rinsed under running distilled water.
  • test pieces were rinsed in the household dishwasher with a formulation consisting of 1 g of surfactant (n-Ci8H37 (OCH2CH2) ioOH) and 20 g of citric acid again with the 55 ° C program to remove any deposits.
  • surfactant n-Ci8H37 (OCH2CH2) ioOH
  • 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 with regard to the inhibition of glass corrosion.
  • Table 2 Results of tests with dishwasher (endurance runner)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Medicinal Preparation (AREA)
  • Washing And Drying Of Tableware (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Formulations contenant (A) au moins un composé sélectionné parmi des aminocarboxylates et des polyaminocarboxylates, (B) au moins un homopolymère ou copolymère d'imine d'éthylène, (C) du citrate de sodium et (D) au moins un composé sélectionné parmi le percarbonate de métal alcalin, le perborate de métal alcalin et le persulfate de métal alcalin.
EP12762614.1A 2011-10-19 2012-09-27 Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation Revoked EP2768935B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP12762614.1A EP2768935B1 (fr) 2011-10-19 2012-09-27 Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation
PL12762614T PL2768935T3 (pl) 2011-10-19 2012-09-27 Preparaty, ich zastosowanie jako środków do zmywania naczyń lub do wytwarzania środków do zmywania naczyń i ich wytwarzanie

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP11185825 2011-10-19
EP12156369 2012-02-21
PCT/EP2012/069040 WO2013056965A1 (fr) 2011-10-19 2012-09-27 Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation
EP12762614.1A EP2768935B1 (fr) 2011-10-19 2012-09-27 Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation

Publications (2)

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EP2768935A1 true EP2768935A1 (fr) 2014-08-27
EP2768935B1 EP2768935B1 (fr) 2017-11-15

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EP12762614.1A Revoked EP2768935B1 (fr) 2011-10-19 2012-09-27 Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation

Country Status (12)

Country Link
EP (1) EP2768935B1 (fr)
JP (1) JP6055480B2 (fr)
KR (1) KR101952567B1 (fr)
CN (1) CN103890159A (fr)
BR (1) BR112014009199A8 (fr)
CA (1) CA2849358A1 (fr)
ES (1) ES2659552T3 (fr)
IN (1) IN2014CN03471A (fr)
MX (1) MX2014004577A (fr)
PL (1) PL2768935T3 (fr)
RU (1) RU2612960C2 (fr)
WO (1) WO2013056965A1 (fr)

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US10301576B2 (en) * 2013-02-28 2019-05-28 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
EP2989192B1 (fr) * 2013-04-23 2018-08-08 Basf Se Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
JP6735671B2 (ja) 2013-09-13 2020-08-05 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ エナンチオマーの混合物、及びその混合物の製造方法
GB201409631D0 (en) 2014-05-30 2014-07-16 Reckitt Benckiser Brands Ltd Improved PEI composition
GB201409632D0 (en) * 2014-05-30 2014-07-16 Reckitt Benckiser Brands Ltd Improved detergent composition
PL3034588T3 (pl) 2014-12-17 2019-09-30 The Procter And Gamble Company Kompozycja detergentu
EP3034596B2 (fr) * 2014-12-17 2021-11-10 The Procter & Gamble Company Composition de détergent
EP3034597A1 (fr) 2014-12-17 2016-06-22 The Procter and Gamble Company Composition de détergent
WO2017167599A1 (fr) 2016-03-30 2017-10-05 Basf Se Concentrés, procédés de fabrication et utilisations
EP3275988B1 (fr) 2016-07-26 2020-07-08 The Procter and Gamble Company Composition de détergent de lave-vaisselle automatique
EP3755782B1 (fr) 2018-02-23 2021-10-13 Unilever Global IP Limited Produit détergent en dose unitaire comportant une partie solide brillante
KR102375253B1 (ko) 2020-06-05 2022-03-16 라이온코리아 주식회사 식기세척기용 액상 세제 조성물
WO2023117494A1 (fr) 2021-12-20 2023-06-29 Basf Se Polymères de polypropylène imine (ppi), leur préparation, leurs utilisations et compositions comprenant de tels ppi

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US5837663A (en) 1996-12-23 1998-11-17 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets containing a peracid
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US5955415A (en) * 1997-08-04 1999-09-21 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polyethyleneimines for enhanced peroxygen bleach stability
US6964943B1 (en) * 1997-08-14 2005-11-15 Jean-Luc Philippe Bettiol Detergent compositions comprising a mannanase and a soil release polymer
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
DE10104469A1 (de) * 2001-02-01 2002-08-08 Basf Ag Copolymere zur Verhinderung von Glaskorrosion
EP1721962B1 (fr) 2005-05-11 2008-08-13 Unilever N.V. Compositions detergentes pour lave vaisselle et procédé pour nettoyer la vaiselle
DE102005041347A1 (de) 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
GB0618402D0 (en) * 2006-09-19 2006-11-01 Reckitt Benckiser Nv Detergent composition and method
GB0625586D0 (en) 2006-12-21 2007-01-31 Reckitt Benckiser Nv Composition
DE102007019458A1 (de) * 2007-04-25 2008-10-30 Basf Se Phosphatfreies Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
CN101848983A (zh) 2007-11-09 2010-09-29 宝洁公司 由包含至少一种烷氧基化油脂清洁聚合物的多聚合物体系组成的清洁组合物
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Also Published As

Publication number Publication date
BR112014009199A8 (pt) 2017-06-20
ES2659552T3 (es) 2018-03-16
EP2768935B1 (fr) 2017-11-15
MX2014004577A (es) 2014-06-23
JP2014534990A (ja) 2014-12-25
BR112014009199A2 (pt) 2017-06-13
CN103890159A (zh) 2014-06-25
RU2014119761A (ru) 2015-11-27
RU2612960C2 (ru) 2017-03-14
KR101952567B1 (ko) 2019-02-27
KR20140088569A (ko) 2014-07-10
JP6055480B2 (ja) 2016-12-27
CA2849358A1 (fr) 2013-04-25
PL2768935T3 (pl) 2018-04-30
WO2013056965A1 (fr) 2013-04-25
IN2014CN03471A (fr) 2015-10-09

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