EP2367920B1 - Détergent pour lave-vaisselle - Google Patents

Détergent pour lave-vaisselle Download PDF

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Publication number
EP2367920B1
EP2367920B1 EP09795392.1A EP09795392A EP2367920B1 EP 2367920 B1 EP2367920 B1 EP 2367920B1 EP 09795392 A EP09795392 A EP 09795392A EP 2367920 B1 EP2367920 B1 EP 2367920B1
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EP
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Prior art keywords
weight
automatic dishwashing
dishwashing detergent
carbonate
group
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EP09795392.1A
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German (de)
English (en)
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EP2367920A1 (fr
Inventor
Dorota SENDOR-MÜLLER
Johannes Zipfel
Arnd Kessler
Christian Nitsch
Sven Müller
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL09795392T priority Critical patent/PL2367920T3/pl
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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

Definitions

  • the present application describes automatic dishwashing detergents, automatic dishwashing processes using these dishwashing detergents and the use of these dishwashing detergents for improving the machine dishwashing cleaning performance.
  • automatic dishwashing detergents In order to obtain spotless dishes, bleaching agents are used in automatic dishwashing detergents. In order to activate these bleaching agents and to achieve an improved bleaching effect during cleaning at temperatures of 60 ° C. and below, automatic dishwashing detergents generally also contain bleach activators or bleach catalysts, with the bleach catalysts in particular having proven to be particularly effective.
  • bleaches are limited due to incompatibilities with other detergent or cleaning active ingredients, such as enzymes, or because of stability issues in the storage of bleach-containing detergents and cleaners. This is especially true for liquid detergents or cleaning agents.
  • the automatic dishwashing detergents intended for the private end user contain builders as the essential ingredient for the cleaning and rinse aid success.
  • these builders increase the alkalinity of the cleaning liquor, whereby fats and oils are emulsified and saponified with increasing alkalinity, and on the other hand reduce the water hardness of the cleaning liquor by complexing the calcium ions contained in the aqueous liquor.
  • Particularly effective builders have proved to be the alkali metal phosphates which, for this reason, form the main constituent of the vast majority of commercially available automatic dishwashing detergents.
  • phosphates are highly valued for their beneficial effect as a component of automatic dishwashing detergents
  • their use is not unproblematical from the environmental point of view since a substantial portion of the phosphate is present in household wastewater the waters get and especially in stagnant water (lakes, barrages) plays a critical role in their over-fertilization.
  • eutrophication the use of pentasodium triphosphate in laundry detergents in a number of countries, eg USA, Canada, Italy, Sweden, Norway, has been considerably reduced by law and regulations. completely prohibited in Switzerland. In Germany, detergents since 1984 may contain no more than 20% of this builder.
  • nitrilotriacetic acid especially sodium aluminosilicates (zeolites) are used as phosphate substitutes or substitutes in textile detergents.
  • these substances are not suitable for use in automatic dishwashing detergents for various reasons.
  • alkali metal phosphates in automatic dishwashing detergents therefore, a number of substitutes are discussed in the literature, of which the citrates are particularly noteworthy.
  • Phosphate-free automatic dishwashing detergents which, in addition to a citrate, furthermore contain carbonates, bleaches and enzymes are described, for example, in the European patents EP 662 117 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).
  • the US 4704233 (Procter & Gamble) discloses bleach-free detergents which include EDDS and carbonate.
  • MGDA methylglycine diacetic acid
  • automatic dishwashing detergents Another technical possibility for improving the cleaning performance of automatic dishwashing detergents is the use of bleaching agents.
  • bleaching agents To activate these bleaching agents and to achieve an improved bleaching action when cleaning at temperatures of 60 ° C and below, automatic dishwashing detergents generally further contain bleach activators or Bleach catalysts, in particular, the bleach catalysts have been found to be particularly effective.
  • bleaches are limited due to incompatibilities with other detergent or cleaning active ingredients, such as enzymes, or because of stability issues in the storage of bleach-containing detergents and cleaners. This is especially true for liquid detergents or cleaning agents.
  • the automatic dishwashing compositions according to the invention are of low alkalinity.
  • Preferred automatic dishwasher detergents according to the invention are characterized in that the automatic dishwashing detergent has a pH (10% solution, 20 ° C.) between 9 and 11.5, preferably between 9.6 and 11.6.
  • a first essential ingredient of the composition of the invention is the citrate.
  • the term "citrate” also includes citric acid as well as its salts, in particular their alkali metal salts.
  • Particularly preferred automatic dishwasher detergents according to the invention contain, based on their total weight, 5 to 50% by weight, preferably 5 to 40% by weight and in particular 5 to 30% by weight of citrate.
  • the dishwasher detergents according to the invention contain, in addition to the citrates, additional carbonates and / or bicarbonates as additional builders.
  • additional carbonates and / or bicarbonates as additional builders.
  • the group of carbonates and bicarbonates is summarized in the context of this application by the name (hydrogen) carbonate.
  • the automatic dishwashing compositions according to the invention contain ethylenediamine disuccinic acid (EDDS), preferred automatic dishwashing agents, characterized in that the automatic dishwashing agent, based on its total weight, 3.0 to 35 wt .-%, preferably 4.0 to 30 wt. % and in particular 8.0 to 25 wt .-% ethylenediamine disuccinic acid.
  • EDDS ethylenediamine disuccinic acid
  • ethylenediamine disuccinic acid includes not only the free acids but also their salts, for example their sodium or potassium salts.
  • EDDS ethylenediamine disuccinic acid
  • the weight ratio of the components (hydrogen) carbonate b) and ethylenediamine disuccinic acid c) used in these agents has proven to be essential.
  • the Teealisms in the machine dishwashing detergent according to the invention can be improved, wherein weight ratios of the components (hydrogen) carbonate b) and ethylenediamine disuccinic acid c) between 3: 5 and 8: 1, preferably between 1: 1 and 6: 1 and in particular between 1: 1 and 4: 1, have proven to be particularly advantageous.
  • Preferred automatic dishwashing detergents are therefore characterized in that, based on their total weight, they contain from 2.0 to 20% by weight, preferably from 2.5 to 15% by weight and in particular from 2.5 to 10% by weight of anionic copolymer, comprising i) one or more polyunsaturated monomers from the group of carboxylic acids ii) one or more polyunsaturated monomers from the group of sulfonic acids iii) optionally contain further ionic or nonionic monomers.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic 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, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
  • the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions.
  • metal ions preferably alkali metal ions and especially sodium ions.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the polymeric sulfonates in addition to carboxyl-containing monomer and sulfonic acid-containing monomer further comprise at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • the agents according to the invention preferably further comprise at least one organic cobuilder.
  • organic co-builders are polycarboxylates / polycarboxylic acids, dextrins and phosphonates. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • these are adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof.
  • NTA nitrilotriacetic acid
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these may be mentioned here.
  • Preferred automatic dishwashing agents according to the invention contain less than 1% by weight, preferably less than 0.5% by weight and in particular less than 0.1% by weight.
  • Methylglycinediacetic acid or its salts.
  • Very particularly preferred automatic dishwasher detergents according to the invention are free of methylglycinediacetic acid or salts thereof.
  • the complex-forming phosphonates comprise a number of different compounds such as, for example, diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the automatic dishwashing compositions of the invention may contain two or more different phosphonates.
  • the proportion by weight of the phosphonates in the total weight of automatic dishwashing detergents according to the invention is preferably from 1 to 8% by weight, preferably from 1.2 to 6% by weight and in particular from 1.5 to 4% by weight.
  • preferred automatic dishwasher detergents according to the invention contain alkali metal hydroxide (s).
  • the alkali metal hydroxides are preferably used in the cleaning agents in amounts below 12% by weight, preferably between 2 and 10% by weight and in particular between 3 and 8% by weight, in each case based on the total weight of the cleaning agent.
  • Preferred automatic dishwasher detergents according to the invention comprise less than 2% by weight, preferably less than 1% by weight and in particular less than 0.5% by weight, of silicate. Very particularly preferred automatic dishwasher detergents according to the invention are silicate-free.
  • dishwashing agents may contain enzyme (s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, as well as improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Washing or cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • a preferably natural polymer or in the form of capsules for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • a preferred machine dishwashing detergent according to the invention is characterized in that the dishwashing detergent, based on its total weight, enzyme preparation in amounts of 0.1 to 12 wt .-%, preferably from 0.2 to 10 wt .-% and in particular from 0.5 to 8 wt .-% contains.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30 Wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0.8 and 10 wt .-% of the enzyme protein.
  • compositions according to the invention may contain further washing or cleaning-active substances, preferably from the group of surfactants, enzymes, organic solvents, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
  • nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • washing or cleaning agents in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation indicated represent statistical averages that may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-2o -alcohol ), preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • C 16-2o -alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Nonionic surfactants which have a melting point above room temperature.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • nonionic surfactants of the general formula in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently stand for integers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula may vary depending on the origin of the alcohol. When native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
  • nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 in which R 1 and R 2 independently of one another represents a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 -alkyl or -alkenyl radical;
  • A, A ', A "and A"' independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention
  • end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits in machine dishwashing can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • the proportion by weight of this specific nonionic surfactant in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.05 and 10% by weight, preferably between 0.1 and 8% by weight, preferably between 0.5 and 5% by weight. % and in particular between 1 and 3 wt .-%.
  • the group of nonionic surfactants of the general formula R 1 O (AlkO) x M (OAlk) y OR 2 comprises a number of particularly preferred compounds.
  • R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30.
  • Appropriate connections can For example, by reacting alkyldiols HO-CHR-CH 2 -OH with ethylene oxide are obtained, followed by a reaction with an Alkylepoxid to close the free OH functions to form a dihydroxy ether.
  • R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2) y OR 2 are in which R 3 and R 4 is H, and the subscripts x and y are preferably independently from each other assume values from 1 to 40, preferably from 1 to 15.
  • R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2) y OR 2 in which the radicals R 1 and R 2 are independently saturated alkyl groups having 4 to 14 Represent carbon atoms and the indices x and y independently of one another assume values of 1 to 15 and in particular of 1 to 12.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
  • the proportion by weight of the nonionic surfactants in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.1 and 15 Wt .-%, preferably between 0.2 and 10 wt .-%, preferably between 0.5 and 8 wt .-% and in particular between 1.0 and 6 wt .-%.
  • organic solvents are derived, for example, from the groups of the monoalcohols, diols, triols or polyols, the ethers, esters and / or amides. Particular preference is given to organic solvents which are water-soluble, "water-soluble" solvents in the context of the present application being solvents which are completely water-soluble at room temperature, ie. without miscibility, are miscible.
  • Organic solvents which can be used in the compositions according to the invention preferably originate from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the given concentration range.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, di ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy trig
  • the organic solvents from the group of the organic amines and / or the alkanolamines have proved to be particularly effective with regard to the cleaning performance and again with regard to the cleaning performance of bleachable soiling, in particular on tea stains.
  • Particularly preferred organic amines are the primary and secondary alkylamines, the alkyleneamines and mixtures of these organic amines.
  • the group of preferred primary alkylamines include monomethylamine, monoethylamine, monopropylamine, monobutylamine, Monopentylamine and cyclohexylamine.
  • the group of preferred secondary alkylamines includes in particular dimethylamine.
  • Preferred alkanolamines are in particular the primary, secondary and tertiary alkanolamines and mixtures thereof.
  • Particularly preferred primary alkanolamines are monoethanolamine (2-aminoethanol, MEA), monoisopropanolamine, diethylethanolamine (2- (diethylamino) ethanol).
  • Particularly preferred secondary alkanolamines are diethanolamine (2,2'-iminodiethanol, DEA, bis (2-hydroxyethyl) amine), N-methyl-diethanolamine, N-ethyl-diethanolamine. Diisopropanolamine and morpholine.
  • Particularly preferred tertiary alkanolamines are triethanolamine and triisopropanolamine.
  • Machine dishwashing detergent characterized in that it, based on its total weight, organic amine and / or alkanolamine, preferably ethanolamine, in amounts of 0.1 to 16 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.5 to 8 wt .-% and in particular from 1.0 to 6 wt .-%, are particularly preferred according to the invention.
  • Formulations 1 to 4 not according to the invention are found in the following tables ( Formulations 1 to 4 not according to the invention ): ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 5 to 60 5 to 50 5 to 40 5 to 30 (Hydrogen) carbonate 1) 2) 2) 3) EDDS 3.0 to 35 3.0 to 35 4.0 to 30 8 to 25 phosphonate 0 to 8 0 to 8 0 to 8 0 to 8 Sulfocopolymer 0 to 20 0 to 20 0 to 20 0 to 20 0 to 20 Nonionic surfactant 0 to 15 0 to 15 0 to 8 0 to 8 Enzyme preparation (s) 0 to 12 0 to 12 0 to 8 0 to 8 Org.
  • Solvent 0.1 to 15 0.2 to 10 0.5 to 8.0 1.0 to 6.0 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Ingredient Recipe 5 [% by weight] Recipe 6 [% by weight] Recipe 7 [% by weight] Recipe 8 [% by weight] citrate 5 to 60 5 to 50 5 to 40 5 to 30 (Hydrogen) carbonate 1) 2) 2) 3) EDDS 3.0 to 35 3.0 to 35 4.0 to 30 8 to 25 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Sulfocopolymer 2 to 20 2.0 to 20 2.0 to 20 2.5 to 15 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 Enzyme preparation (s) 0.1 to 12 0.2 to 10 0.2 to 10 0.5 to 8 Org.
  • the automatic dishwasher detergents according to the invention can be present in the ready-to-use form known to the person skilled in the art, that is to say, for example, in solid or liquid form but also as a combination of solid and liquid supply forms.
  • Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms.
  • the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.
  • Inventive agents can be formulated as single-phase or multi-phase products.
  • automatic dishwashing detergents with one, two, three or four phases are preferred.
  • Machine dishwashing detergents characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
  • the individual phases of multiphase agents may have the same or different states of matter.
  • Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred.
  • Particularly preferred are in particular two- or multi-phase tablets, for example two-layer tablets, in particular two-layer tablets with a trough and a mold body located in the trough.
  • Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
  • the automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • disintegration aids so-called tablet disintegrants
  • Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain.
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • the group of preferred secondary alkylamines includes in particular dimethylamine.
  • Preferred alkanolamines are in particular the primary, secondary and tertiary alkanolamines and mixtures thereof.
  • Particularly preferred primary alkanolamines are monoethanolamine (2-aminoethanol, MEA), monoisopropanolamine, diethylethanolamine (2- (diethylamino) ethanol).
  • Particularly preferred secondary alkanolamines are diethanolamine (2,2'-iminodiethanol, DEA, bis (2-hydroxyethyl) amine), N-methyl-diethanolamine, N-ethyl-diethanolamine. Diisopropanolamine and morpholine.
  • Particularly preferred tertiary alkanolamines are triethanolamine and triisopropanolamine.
  • Machine dishwashing detergent characterized in that it, based on its total weight, organic amine and / or alkanolamine, preferably ethanolamine, in amounts of 0.1 to 15 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.5 to 8 wt .-% and in particular from 1.0 to 6 wt .-%, are particularly preferred according to the invention
  • the automatic dishwashing compositions according to the invention are in liquid form.
  • Preferred liquid dosage forms are based on an aqueous matrix which optionally has proportions of organic solvents.
  • Solvent 0 to 15 0 to 15 0 to 15 0 to 15 0 to 15 phosphate - - - - bleach - - - - water 20 to 80 20 to 80 30 to 70 40 to 60 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Ingredient Recipe 5 [% by weight] Recipe 6 [% by weight] Recipe 7 [% by weight] Recipe 8 [% by weight] citrate 5 to 60 5 to 50 5 to 40 5 to 30 (Hydrogen) carbonate 1) 2) 2) 3) EDDS 3.0 to 35 3.0 to 35 4.0 to 30 8 to 25 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Sulfocopolymer 2 to 20 2.0 to 20 2.0 to 20 2.5 to 15 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 Enzyme preparation (s) 0.1 to 12 0.1 to 12 0.5 to 8 0.5 to 8 Org.
  • these agents preferably contain from 20 to 80% by weight, preferably from 30 to 70% by weight and in particular from 40 to 60% by weight, of water.
  • the metering units of these liquid supply forms preferably comprise the amount of washing or cleaning-active substances necessary for a cleaning cycle.
  • preferred Liquid metering units have a weight between 25 and 60 g, preferably between 30 and 55 g and in particular between 55 and 50 g.
  • the dishwasher detergents according to the invention exhibit their advantageous cleaning and drying properties, in particular also in low-temperature cleaning processes.
  • Preferred dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C.
  • agents according to the invention are distinguished from conventional automatic dishwasher detergents by improved tea cleaning.
  • Another object of the present application is therefore the use of a machine dishwashing detergent according to the invention for improving the dough cleaning in automatic dishwashing.
  • soiled dishes were rinsed in a dishwashing machine (Miele G 698) at a water hardness of 21 ° dH and a temperature of 50 ° C. with 42.5 g ml of the automatic dishwashing detergent listed in the table below.

Claims (15)

  1. Agent de lavage pour lave-vaisselle faiblement alcalin sans phosphate ni agent de blanchiment, contenant :
    a) 5 à 60% en poids de citrate, le terme « citrate » désignant l'acide citrique ainsi que leurs sels,
    b) un (hydrogéno)carbonate,
    c) 2 à 40% en poids acide d'éthylène-diamine-disuccinique,
    caractérisé en ce que le rapport en poids des composants b) et c) est compris entre 1:5 et 10:1, et que l'agent de lavage pour lave-vaisselle contient, sur la base de son poids total, de 2,0 à 20% en poids d'un copolymère anionique, comprenant
    i) un ou plusieurs monomères polyinsaturés choisis comportant les acides carboxyliques,
    ii) un ou plusieurs monomères polyinsaturés choisis dans le groupe comportant les acides sulfoniques,
    iii) éventuellement d'autres monomères ioniques ou non ioniques.
  2. Agent de lavage pour lave-vaisselle selon la revendication 1, caractérisé en ce que l'agent de lavage pour lave-vaisselle contient, sur la base de son poids total, 5 à 50% en poids, de préférence 5 à 40% en poids et en particulier 5 à 30% en poids, de citrate.
  3. Agent de lavage pour lave-vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent de lavage pour lave-vaisselle contient, sur la base de son poids total, 2,0 à 50% en poids d'(hydrogéno)carbonate, de préférence 4,0 à 45% en poids d'(hydrogéno)carbonate, et en particulier 8,0 à 40% en poids de d'(hydrogéno)carbonate.
  4. Agent de lavage pour lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de lavage pour lave-vaisselle contient, sur la base de son poids total, 3,0 à 35% en poids, de préférence 4,0 à 30% en poids, plus préférablement 8,0 à 25% en poids, d'acide éthylène-diamine-disuccinique.
  5. Agent de lavage pour lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que le rapport en poids des composants b) et c) est compris entre 3:5 et 8:1, de préférence entre 1:1 et 6:1 et en particulier entre 1:1 et 4:1.
  6. Agent de lavage pour lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de lavage pour lave-vaisselle contient, sur la base de son poids total, 2,5 à 15% en poids, en particulier 2,5% à 10% en poids, d'un copolymère anionique comprenant
    i) un ou plusieurs monomères polyinsaturés choisis dans le groupe comportant les acides carboxyliques,
    ii) un ou plusieurs monomères polyinsaturés choisis dans le groupe comportant les acides sulfoniques,
    iii) éventuellement d'autres monomères ioniques ou non ioniques.
  7. Agent de lavage pour lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de lavage pour lave-vaisselle contient, sur la base de son poids total, une composition enzymatique dans des quantités de 0,1 à 12% en poids, de préférence de 0,2 à 10% en poids et en particulier de 0,5 à 8% en poids.
  8. Agent de lavage pour lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de lavage pour lave-vaisselle contient, sur la base de son poids total, 1 à 8% en poids, de préférence 1,2 à 6% en poids, plus préférablement 1,5 à 4% en poids, de phosphonate.
  9. Agent de lavage pour Lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de lavage pour lave-vaisselle contient, par rapport à son poids total, un tensioactif non ionique dans des quantités de 0,1 à 15% en poids, de préférence 0,2 à 10% en poids, de façon particulièrement préférée de 0,5 à 8% en poids, et en particulier de 1,0 à 6% en poids.
  10. Agent de lavage pour lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de lavage pour lave-vaisselle contient un tensioactif non ionique de la formule générale R1O(AlkO)xM(OAlk)yOR2, dans laquelle
    - R1 et R2 représentent indépendamment un radical alkyle ramifié ou non ramifié, saturé ou insaturé, éventuellement hydroxylé ayant 4 à 22 carbone ;
    - Alk représente un radical alkyle ramifié ou non ramifié ayant 2 à 4 atomes de carbone ;
    - x et y ont indépendamment des valeurs comprises entre 1 et 70 ; et
    - M représente un radical alkyle choisi dans le groupe comportant CH2, CHR3, CR3R4, CH2CHR3, et CHR3CHR4, où R3 et R4 représente indépendamment un groupe alkyle ramifié ou non ramifié, saturé ou insaturé ayant 1 à 18 atomes de carbone.
  11. Agent de lavage pour lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de lavage pour lave-vaisselle contient, sur la base de son poids total, une amine organique et/ou une alcanolamine, de préférence une éthanolamine, dans des quantités de 0,1 à 15% en poids, de préférence de 0,2 à 10% en poids, de préférence de 0,5 à 8% en poids et en particulier de 1,0 à 6% en poids.
  12. Agent de lavage pour lave-vaisselle selon l'une des revendications précédentes, contenant
    a) 5% à 40% en poids de citrate,
    b) 0,1% à 8% en poids de composition enzymatique amylase et/ou protéase,
    c) 4,0 à 30% en poids d'acide éthylène-diamine-disuccinique,
    d) un (hydrogéno)carbonate
    e) 2,0 à 20% en poids de copolymère anionique, comprenant
    i) un ou plusieurs monomères polyinsaturés choisis dans le groupe comportant les acides carboxyliques,
    ii) un ou plusieurs monomères polyinsaturés choisis dans le groupe comportant les acides sulfoniques,
    iii) éventuellement d'autres monomères ioniques ou non ioniques,
    f) 0,2 à 10% en poids de tensioactif non ionique,
    caractérisé en ce que le rapport en poids des composants b) et c) est compris entre 1:1: et 6:1.
  13. Agent de lavage pour lave-vaisselle selon l'une des revendications précédentes, comprenant
    a) 5 à 40% en poids de citrate,
    b) 0,1 à 8% de composition enzymatique amylase et/ou protéase,
    c) 4,0 à 30% en poids d'acide éthylène-diamine-disuccinique
    d) un (hydrogéno)carbonate
    e) 2,0 à 20% en poids de copolymère anionique comprenant
    i) un ou plusieurs monomères polyinsaturés choisis dans le groupe comportant les acides carboxyliques,
    ii) un ou plusieurs monomères polyinsaturés choisis dans le groupe comportant les acides sulfoniques,
    iii) éventuellement d'autres monomères ioniques ou non ioniques,
    f) 0,2 à 10% en poids d'un tensioactif non ionique,
    g) 20 à 70% en poids d'eau,
    caractérisé en ce que le rapport en poids des composants b) et c) est compris entre 1:1 et 6:1.
  14. Procédé de nettoyage de la vaisselle dans un lave-vaisselle, à l'aide d'un agent de lavage pour lave-vaisselle selon l'une des revendications précédentes.
  15. Utilisation d'un agent de lavage pour lave-vaisselle selon l'une des revendications précédentes pour améliorer le nettoyage du thé lors du lavage dans un lave-vaisselle.
EP09795392.1A 2008-12-19 2009-12-14 Détergent pour lave-vaisselle Active EP2367920B1 (fr)

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DE102008063801A1 (de) 2010-06-24
US20110240063A1 (en) 2011-10-06
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PL2367920T3 (pl) 2016-06-30
US8268768B2 (en) 2012-09-18
WO2010069905A1 (fr) 2010-06-24

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