EP3068859B1 - Composition detergente pour lave vaiselle et son utilisation - Google Patents

Composition detergente pour lave vaiselle et son utilisation Download PDF

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Publication number
EP3068859B1
EP3068859B1 EP14796713.7A EP14796713A EP3068859B1 EP 3068859 B1 EP3068859 B1 EP 3068859B1 EP 14796713 A EP14796713 A EP 14796713A EP 3068859 B1 EP3068859 B1 EP 3068859B1
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Prior art keywords
weight
dishwashing agent
acid
formula
agent according
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German (de)
English (en)
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EP3068859A1 (fr
Inventor
Johannes Himmrich
Joachim Erbes
Stefan RIEGELBECK
Günther Schimmel
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Catexel Production GmbH
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Weylchem Wiesbaden GmbH
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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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0047—Other compounding ingredients characterised by their effect pH regulated compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O

Definitions

  • the present invention relates to dishwashing detergents, as well as the use of these detergents, in particular in automatic dishwashing.
  • Modern machine dishwashing detergents are subject to a large number of requirements. They are intended to show improved cleaning and rinsing performance, even in low-temperature cleaning operations or in cleaning operations with reduced water consumption. Particular attention is paid to the drying properties of the automatic dishwashing detergents used. The need for additional manual drying of the cleaned dishes is undesirable, dripping and residue on the treated dishes should be avoided.
  • machine dishwashing detergents should be environmentally compatible and, if possible, should not contain any phosphate-containing constituents, in particular phosphate builders.
  • MGDA methylglycine diacetic acid
  • Machine dishwashing detergents containing MGDA are described, for example, in the European patent EP 906 407 B1 (Reckitt Benckiser) or in the European patent application with the disclosure number EP 1 113 070 A2 (Reckitt Benckiser).
  • This application was therefore based on the object to provide automatic dishwashing detergent with improved cleaning and rinsing performance and good deposit-inhibiting effect.
  • Crystalline layered silicates according to formula (1) are described, for example, in European patent application with the disclosure number EP 0 164 514 A1 described.
  • Preferred crystalline layered silicates are those in which x in the abovementioned general formula assumes the values 1.9 to 3.5.
  • Beta-disodium silicates having a molar ratio of SiO 2 / Na 2 O between 1, 9 and 3.2 can be prepared according to Japanese Patent Application Laid-Open Nos JP 04/238 809 A or JP 04/260 610 A getting produced. Also prepared from amorphous silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula (1), in which x is a number from 1.9 to 2.1, can be used.
  • a crystalline sodium layer silicate with a molar ratio of SiO 2 / Na 2 O of 1.8 to 3 is used.
  • the crystalline layered disodium disilicate of the builder a) is composed of varying percentages of the polymorphic phases alpha, beta and delta.
  • amorphous portions may also be present.
  • x can also be odd in commercial products.
  • alpha, beta and delta disodium disilicate are known and may be, for example, the EP 0 164 514 A1 are removed, as has been explained below.
  • the disodium disilicate is preferably a layered crystalline disodium disilicate which consists of at least one of the polymorphic phases of disodium disilicate and of sodium silicates of non-layered silicate nature.
  • crystalline sodium layer silicates having a content of from 80 to 100% by weight of delta-disodium disilicate.
  • crystalline sodium layer silicates having a content of 70 to 100% by weight of beta disodium disilicate.
  • Crystalline sodium layer silicates used with particular preference contain 1 to 40% by weight of alpha disodium disilicate, 0 to 50% by weight, in particular 0 to 45% by weight, of beta disodium disilicate, 50 to 98% by weight of delta disodium disilicate and 0 to 40 wt .-% of non-layered silicate sodium silicates (amorphous portions).
  • Very particularly preferably used crystalline layered sodium silicates contain 7 to 21 wt .-% alpha disodium disilicate, 0 to 12 wt .-% beta disodium disilicate, 65 to 95 wt .-% delta disodium disilicate and 0 to 20 wt .-% amorphous shares.
  • the aforementioned alpha disodium disilicate corresponds to that in the EP 0 164 514 A1 described Na-SKS-5, characterized by the reproduced there X-ray diffraction data, which are assigned to the alpha-Na 2 Si 2 O 5 .
  • the X-ray diffraction patterns are registered with the Joint Committee of Powder Diffraction Standards under the numbers 18-1241, 22-1397, 22-1397A, 19-1233, 19-1234 and 19-1237.
  • the aforementioned beta-disodium disilicate corresponds to that in the EP 0 164 514 A1 described Na-SKS-7, characterized by the reproduced there X-ray diffraction data, which are assigned to the beta-Na 2 Si2O 5 .
  • the X-ray diffraction patterns are registered with the Joint Committee of Powder Diffraction Standards under numbers 24-1123 and 29-1261.
  • the aforementioned delta-disodium disilicate corresponds to that in the EP 0 164 514 A1 described Na-SKS-6, characterized by the reproduced there X-ray diffraction data, which are assigned to the delta-Na 2 Si 2 O 5 .
  • the X-ray diffraction diagrams are registered with the Joint Committee of Powder Diffraction Standards under the number 22-1396.
  • compositions according to the invention contain crystalline sodium layer silicate of the formula (1) in granulated form, and also cogranulates containing crystalline sodium layer silicate and sparingly soluble metal carbonate, such as, for example, in US Pat WO2007 / 101622 A1 described.
  • compositions according to the invention contain crystalline sodium disilicates Na 2 Si 2 O 5 .yH 2 O with y being 0 to 2.
  • the crystalline layered sodium silicates additionally contain cationic and / or anionic constituents.
  • the cationic constituents are preferably combinations of alkali metal and / or alkaline earth metal cations and / or Fe, W, Mo, Ta, Pb, Al, Zn, Ti, V, Cr, Mn, Co and / or Ni.
  • the anionic constituents are preferably aluminates, sulfates, fluorides, chlorides, bromides, iodides, carbonates, bicarbonates, nitrates, hydrated oxides, phosphates and / or borates.
  • the crystalline layered sodium silicates based on the total content of SiO 2 , contain up to 10 mol% of boron.
  • the crystalline layered sodium silicates based on the total content of SiO 2 , contain up to 20 mol% of phosphorus.
  • Sodium disilicates of the formula beta-Na 2 Si 2 O 5 prepared by hydrothermal methods are also particularly preferred, as described in the patent documents WO 92/09526 A1 . US-A-5,417,951 . DE 41 02 743 A1 and WO 92/13935 A1 to be discribed.
  • sodium layer silicates are those according to WO 00/09444 A1 especially prefers.
  • sodium layer silicates are also those according to EP 0 550 048 A1 and EP 0 630 855 A1 prefers
  • compositions according to the invention may contain, in addition to crystalline sodium layer silicate according to the formula (1), further water-soluble organic and / or inorganic builders.
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polymeric alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • amorphous sodium silicates having a molar ratio of Na 2 O: SiO 2 of from 1: 1 to 1: 3.5 can be used.
  • the water-soluble organic builder substances include polycarboxylic acids or their salts, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid or its salt (MGDA), glutamic diacetic acid or its salt (GLDA) and ethylenediamine disuccinic acid or its salt (EDDS), nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid.
  • Polyphosphonic acids in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, may also be used.
  • Preferred builders or co-builders are also polycarboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins, as in US Pat WO 93/16110 A1 .
  • WO 92/18542 A1 or EP 0 232 202 A2 described as well as polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which einpoly-polymerized even small amounts of polymerizable substances without carboxylic acid functionality can contain.
  • the average molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200 000, that of the copolymers between 2000 and 200 000, preferably between 50 000 to 120 000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has an average molecular weight of 50,000 to 100,000.
  • Commercially available products are, for example, Sokalan® CP 5, Sokalan® CP 10 and PA 30 from BASF.
  • copolymers of acrylic acid or methacrylic acid with vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid, preferably from a C 3 -C 4 -monocarboxylic acid, in particular of (meth) acrylic acid, where the second acidic monomer or its Salt may be a derivative of a C 2 -C 6 dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl or aryl radical.
  • Such polymers can be prepared in particular by methods described in the German patent documents DE 42 21 381 and DE 43 00 772 are generally described, and generally have a molecular weight between 1000 and 200,000. Further preferred copolymers are those described in German patent applications with the disclosure number DE 43 03 320 A1 and DE 44 17 734 A1 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 wt .-% aqueous solutions are used. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • water-soluble builder components in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the above-mentioned type of polycarboxylates, which act as co-builders in hard water regions, and naturally occurring hydroxycarboxylic acids, such as mono-, dihydroxysuccinic acid, alpha- Hydroxypropionic acid and gluconic acid.
  • the salts of citric acid especially sodium citrate, both anhydrous trisodium citrate, and trisodium citrate dihydrate can be used.
  • compositions according to the invention When used as dishwashing agents, the compositions according to the invention exhibit pronounced detergency when, in addition to crystalline sheet silicate of formula (1), they additionally contain builders selected from methylglycinediacetic acid or its salts, sodium polyphosphate (NTP) and / or sodium citrate.
  • builders selected from methylglycinediacetic acid or its salts, sodium polyphosphate (NTP) and / or sodium citrate.
  • compositions according to the invention contain bleach catalysts according to the formula (2) wherein a is 1 or 2, b is a number from 0 to 4, X is any monovalent to divalent anion, preferably PF 6 - , CH 3 COO - , Cl - , SO 4 2- , and in particular PF 6 - stands.
  • compositions according to the invention contain the bleach catalyst bis (N, N ', N "-trimethyl-1,4,7-triazacyclononane) -trioxo-dimangane (IV) di (hexafluorophosphate) monohydrate, which is known as Peractive® MnTACN is available.
  • compositions according to the invention comprise the bleach catalyst ⁇ -manganese oxalate dihydrate according to the formula (3) as in J. Soleimannejad et al., Acta Cryst. (2007) E63, m 2389 - m 2390 described and available as Peractive® MnOx.
  • Formula (3) corresponds to (OOC-COO) Mn (2H 2 O) (OOC-COO) Mn (2H 2 O) (OOC-COO).
  • Bleaching agents are, on the one hand, compounds which react with bleach activators to form peroxyacids which bleach much more effectively at low temperatures (e.g., ⁇ 70 ° C) than the bleaches alone.
  • Suitable bleaching agents are hydrogen peroxide and inorganic persalts, preferably percarbonates, perborates, persulfates and persilicates, in particular in the form of alkali metal salts.
  • Particularly preferred such bleaching agents are hydrogen peroxide, sodium perborate (monohydrate and tetrahydrate) and / or sodium percarbonate, particularly preferably sodium perborate (monohydrate and tetrahydrate) and / or sodium percarbonate.
  • the one or more bleaching agents are selected from the group consisting of sodium perborate (monohydrate and tetrahydrate) and sodium percarbonate.
  • Bleaching agents are, on the other hand, compounds which act without a bleach activator. Suitable such bleaching agents are peracids or their salts.
  • peracids or peracid salts are peroxycarboxylic acids and their salts according to the formula wherein R is an alkyl group, aralkyl group, cycloalkyl group, aryl group or heterocyclic group, preferably a linear or branched, substituted or unsubstituted alkyl group, particularly preferably an alkyl group having 6 to 9 carbon atoms, and X + is a suitable counterion, preferably an H + , Potassium or sodium ion. Preference is given to peroxyhexanoic acid, peroxyheptanoic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid and salts thereof.
  • peracids or peracid salts are peroxysulfonic acids and their salts according to the formula wherein R is an alkyl group, aralkyl group, cycloalkyl group, aryl group or heterocyclic group, preferably a linear or branched, substituted or unsubstituted alkyl group, particularly preferably an alkyl group having 6 to 9 carbon atoms, and X + is a suitable counterion, preferably H + , a potassium or sodium ion.
  • peracids or peracid salts are peroxophthalic acids and their salts, phthalimino peracids and their salts, diperoxycarboxylic acids and their salts or peroxy-sulfuric acids and their salts.
  • the bleaching agents which have no bleach activator, particular preference is given to the peracids or salts thereof selected from the group consisting of monoperoxyphthalic acid and its salts, N, N-phthaloylaminoperoxycaproic acid (PAP) and its salts, diperazelaic acid and its salts, diperdodecanedioic acid and their salts and monoperoxy-sulfuric acid and their salts, the salts preferably being selected from the sodium and / or potassium salts.
  • PAP N-phthaloylaminoperoxycaproic acid
  • PAP N-phthaloylaminoperoxycaproic acid
  • diperazelaic acid and its salts diperdodecanedioic acid and their salts
  • monoperoxy-sulfuric acid and their salts the salts preferably being selected from the sodium and / or potassium salts.
  • monoperoxy sulfuric acid and its salts in particular, the potassium peroxymonosulfate (available under the
  • the quantities of bleach used are generally chosen so that in the solutions of the compositions when used as automatic dishwashing detergent during the rinsing process between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm of active oxygen are present.
  • the amount of the one or more bleach catalysts in the compositions of the invention is from 0.01 mmol to 25 mmol, preferably 0.1 mmol to 2 mmol bleach catalyst per mole of bleach.
  • compositions of the invention contain one or more bleach activators.
  • Bleach activators are compounds which release peroxycarboxylic acids under perhydrolysis conditions.
  • compositions according to the invention preferably contain acylated alkylenediamines, in particular tetraacetylethylenedianim (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates, in particular Nonanoyl, isononanoyl or lauroylbenzene sulfonate (NOBS, ISONOBS or LOBS) or their amido derivatives (eg NACAOBS), acylated hydroxycarboxylic acids, such as acetylsalicylic acid or nonanoyloxybenzoic acid (NOBA) and decanoyloxybenzoic acid (TAED), acylated glycolurils, in particular tetraace
  • the compositions contain acylated alkylenediamines, in particular tetraacetylethylenedianim (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT ), acylated phenylsulfonates, especially nonanoyl, isononanoyl or lauroylbenzenesulfonate (NOBS, ISONOBS or LOBS) or their amido derivatives (eg NACAOBS), acylated hydroxycarboxylic acids such as acetylsalicylic acid or nonanoyloxybenzoic acid (NOBA) and decanoyloxybenzoic acid (DOBA)
  • TAED tetraacetylethylenedianim
  • TAGU t
  • compositions contain acylated alkylenediamines, in particular tetraacetylethylenedianim (TAED).
  • TAED tetraacetylethylenedianim
  • compositions according to the invention contain TAED and one of the bleach catalysts according to the above-mentioned formula (2) and preferably in a mixing ratio of 20: 1 to 1: 1, more preferably 15: 1 to 2: 1, and most preferably 10: 1 to 3: 1.
  • compositions of the invention contain one or more bleach activators in an amount of 0.1 to 10 wt .-%, preferably 0.5 to 8 wt .-%, particularly preferably 1 to 6 wt .-%, each based on the total weight of the inventive compositions.
  • compositions according to the invention comprise one or more pH regulators.
  • the compositions according to the invention preferably contain alkali metal carbonates, in particular sodium carbonate, alkali hydrogen carbonates, alkali metal hydroxides, in particular potassium hydroxide and sodium hydroxide, disilicates and amino acids.
  • inorganic acids such as the mineral acids, eg. Hydrochloric acid
  • organic acids for example saturated or unsaturated mono-, di- and tricarboxylic acids and hydroxycarboxylic acids having one or more hydroxy groups, e.g. As citric acid, glycolic acid, lactic acid, maleic acid, formic acid and acetic acid, amidosulfuric, C 6 -C 22 fatty acids and anionic sulfonic acids, and mixtures thereof are used.
  • the compositions contain one or more pH regulators in amounts of from 1 to 40% by weight, in particular from 2 to 30% by weight, based on the total weight of the compositions according to the invention.
  • compositions of the invention may contain one or more surfactants, in particular anionic surfactants and nonionic surfactants and mixtures thereof, but also zwitterionic and amphoteric surfactants in question.
  • surfactants in particular anionic surfactants and nonionic surfactants and mixtures thereof, but also zwitterionic and amphoteric surfactants in question.
  • compositions according to the invention may contain alkyl ether carboxylates R- (OCH 2 CH 2 ) x OCH 2 COOM, where R is an alk (en) yl radical having 12 to 18 carbon atoms and x is a number from 2 to 5.
  • anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • Anionic surfactants are preferably present in the compositions according to the invention in amounts of from 0 to 10% by weight and in particular in amounts of from 0.5 to 5% by weight.
  • Preferred nonionic surfactants in the compositions according to the invention are alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 12 moles of ethylene oxide (EO) and 2 to 17 moles of ethylene oxide (EO) / propylene oxide (PO) are used per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. B.
  • degrees of ethoxylation and degrees of propoxylation given above represent statistical averages which may be an integer or a fractional number for a particular product.
  • compositions of the invention may advantageously Alkylglykoside 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 a glycose unit having 5 or 6 carbon atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number which, as the size to be determined analytically, can also be fractions, between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (VIII) are present, in the radical R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and Z is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups ,
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (IX) in R 3 is a linear or branched alkyl or alkenyl radical having 7 to 21 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 6 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or an aryl radical or a Oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred, and Z is a linear polyhydroxyalkyl radical whose alkyl chain having at least two Is substituted hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • Z is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-allyloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters , preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide and of the fatty acid alkanolamide type may also be suitable according to the invention.
  • the proportion by weight of the one or more nonionic surfactants in the total weight of the compositions according to the invention is preferably 0.1 to 10 wt .-%, preferably 0.5 to 8 wt .-%, particularly preferably 1 to 6 wt .-%.
  • compositions according to the invention comprise one or more enzymes selected from proteases, amylases, mannases, lipases, endolases, pectinases, cellulases, pullinases, cutinases or peroxidases.
  • proteases available are Liquanase® Ultra 2.0 XL, BLAP®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purafect®, OxP and / or Duraxym®.
  • amylases for example Stainzyme® Plus 12L, Termamyl®, Amylase® LT, Maxamyl®, Duramyl® and / or Pruafect® Ox, Mannasen, for example, Mannaway 4.0 L, lipases, for example Lipex® 100 L, Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, on endolases, for example Endolase® 5000L, at pectinases for example Pectinex 3X L and / or Pectinex Ultra SPL and on cellulases, for example Carezyme 1000 L and / or Celluclast 1.5 L.
  • lipases for example Lipex® 100 L, Lipolase®, Lipomax®, Lumafast® and / or Lipozym®
  • endolases for example Endolase® 5000L
  • pectinases for example Pectinex 3X L and / or Pectinex Ultra SPL and on cellulases, for
  • the proportion by weight of the one or more enzymes in the total weight of the compositions according to the invention is preferably from 0.001 to 8% by weight, more preferably from 0.001 to 4.5% by weight and most preferably from 0.01 to 3.5% by weight. %.
  • compositions according to the invention contain crystalline sodium layer silicate of the formula (1) in the form of a compound containing crystalline sodium layer silicate of the formula (1) and an acidic component.
  • the acidic component is preferably polycarboxylates, in particular a not or only partially neutralized homo- and / or copolymer of acrylic acid, methacrylic acid, maleic acid, polyaspartic acid, sugar carboxylic acid and / or further monomers.
  • the molecular weight of the homopolymers and the copolymers is preferably in the range of 1000 to 100,000 g / mol, more preferably 2,000 to 50,000 g / mol.
  • Particularly preferred are acrylic acid / maleic acid copolymers having a molecular weight of 4,000 to 50,000 g / mol.
  • Prefers are also copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl ester, ethylene, propylene and styrene.
  • Sokalan TM CP 5 and PA 30 from BASF, Alcosperse TM 175 or 177 from Alco, and LMW 45 N and SP02 N from Norsohaas.
  • the weight ratio of alkaline silicate to acidic polycarboxylate is 40 to 1 to 1, preferably 20 to 2 to 1.
  • compositions according to the invention contain crystalline layered sodium disilicate / copolymer compound based on acrylic acid / maleic acid, which is obtainable, for example, as SKS®-6 HD from Clariant GmbH.
  • compositions according to the invention may contain further components, such as electrolytes, silver corrosion inhibitors, foam regulators, for example chlorine-stable phosphoric acid esters, such as triisobutyl phosphate (defoamer TIP from Clariant GmbH), or known silicones such as SP types from Wacker Chemie GmbH, disintegrants, and colorants Contain fragrances.
  • foam regulators for example chlorine-stable phosphoric acid esters, such as triisobutyl phosphate (defoamer TIP from Clariant GmbH), or known silicones such as SP types from Wacker Chemie GmbH, disintegrants, and colorants Contain fragrances.
  • compositions according to the invention may both contain phosphate as well as be phosphate-free.
  • compositions according to the invention are phosphate-free.
  • compositions according to the invention When used as automatic dishwashing agents, the compositions according to the invention have a very good cleaning performance and are distinguished by a reduced deposit formation, in particular by reduced staining and film formation. Significant is the synergistically enhanced detergency of the combination of crystalline layered silicate and bleach catalyst over oatmeal / chocolate soils.
  • compositions according to the invention are preferably in the form of pulverulent, granular or tablet-form preparations which can be prepared in a conventional manner, for example by mixing, granulating, roll compacting and / or spray-drying.
  • the invention relates to a method for cleaning surfaces, in particular dishes and glasses.
  • the method comprises contacting the composition according to the invention with water and with the surface to be cleaned, in particular with dishes and glasses, and the action of the aqueous cleaning liquid formed on the surface to be cleaned.
  • the invention moreover relates to the use of the compositions according to the invention as dishwashing agents, in particular as automatic dishwasher detergent.
  • Example 1 (automatic dishwashing detergent according to the invention)
  • Example 3 (automatic dishwashing detergent without crystalline layered silicate)
  • Example 5 (automatic dishwashing detergent according to the invention, sodium citrate)
  • Example 6 (automatic dishwashing detergent according to the invention, sodium citrate)
  • Example 7 (automatic dishwashing detergent according to the invention, sodium triphosphate)
  • composition % By weight (tel quel) SKS® 6 granules 12 Peractive® MnTACN 0,015 sodium citrate 20 sodium 25.5 Sokalan® PA3OCL 6 sodium 15 Genapol EP 2544 1.5 Blaze evity® 100T 0.7 Stainzyme® 12T 0.6 sodium sulphate 17.685
  • the cleaning performance was evaluated. This was done visually on the teacups and on egg yolk soiling by weighing the plates before and after cleaning.
  • the degree of purification of the melamine plates was determined by differential whiteness measurement at 457nm.
  • Table 1 Cleaning performance of the formulations according to Example 1, 2 and 3 Formulation Example No. 1 2 3 Cleaning performance in% tea 94 65 73 egg yolk 80 77 63 Starch mixed 44 40 37 Oatmeal / chocolate 10 6 1
  • the glasses were visually assessed in a box lined with black felt and illuminated from the inside ("black box").
  • the glasses rinsed with the formulation 1 according to the invention have an undamaged, high-gloss surface, while those washed with the dishwashing detergent of the formulation according to Example 4, which is characterized in that crystalline sodium disilicate was replaced by amorphous sodium disilicate, rinsed glasses Gloss turbidity and partly Have line corrosion effects.

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Claims (21)

  1. Produit vaisselle contenant les composants
    a) 10 à 90% en poids d'un ou de plusieurs adjuvants, au moins 10% en poids, par rapport à la quantité totale du ou des adjuvants, étant constitués par du silicate sodique cristallin à couches de formule (1)

            Na2SixO2x+1 · y H2O     formule (1)

    dans laquelle x représente un nombre de 1,9 à 4 et y un nombre de 0 à 20,
    b) 0,0025 à 2,0000% en poids d'un ou de plusieurs catalyseurs de blanchiment contenant la formule (2)
    Figure imgb0012
     dans laquelle a représente 1 ou 2, b représente un nombre de 0 à 4, X représente un anion quelconque monovalent un divalent,
    c) 0,1 à 20% en poids d'un ou de plusieurs agents de blanchiment contenant de l'oxygène,
    d) 0 à 10% en poids d'un ou de plusieurs activateurs de blanchiment,
    e) 1 à 85% en poids d'un ou de plusieurs régulateurs du pH,
    f) 0 à 10% en poids d'une ou de plusieurs substances tensioactives,
    g) 0 à 5% en poids d'une ou de plusieurs enzymes,
    les indications de quantité des composants a) à g) se rapportant à la quantité totale de la composition.
  2. Produit vaisselle contenant les composants
    a) 10 à 90% en poids d'un ou de plusieurs adjuvants, au moins 10% en poids, par rapport à la quantité totale du ou des adjuvants, étant constitués par du silicate sodique cristallin à couches de formule (1)

            Na2SixO2x+1 · y H2O     formule (1)

    dans laquelle x représente un nombre de 1,9 à 4 et y un nombre de 0 à 20,
    b) 0,0025 à 2,0000% en poids d'un ou de plusieurs catalyseurs de blanchiment contenant de l'α-oxalate de manganèse dihydraté,
    c) 0,1 à 20% en poids d'un ou de plusieurs agents de blanchiment contenant de l'oxygène,
    d) 0 à 10% en poids d'un ou de plusieurs activateurs de blanchiment,
    e) 1 à 85% en poids d'un ou de plusieurs régulateurs du pH,
    f) 0 à 10% en poids d'une ou de plusieurs substances tensioactives,
    g) 0 à 5% en poids d'une ou de plusieurs enzymes,
    les indications de quantité des composants a) à g) se rapportant à la quantité totale de la composition et la composition étant exempte de phosphates.
  3. Produit vaisselle selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le silicate sodique cristallin à couches de la formule (1) est composé de proportions variables, en pour cent, de phases polymorphes alpha, bêta et delta.
  4. Produit vaisselle selon l'une quelconque des revendications 1 à 3, caractérisé en ce que 1,9 ≤ x ≥ 2,2.
  5. Produit vaisselle selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il contient du silicate sodique cristallin à couches de formule (1) sous forme granulée ainsi que des cogranulats, contenant le silicate sodique cristallin à couches de formule (1) et du carbonate métallique peu soluble.
  6. Produit vaisselle selon l'une quelconque des revendications 1 à 5, caractérisé en ce que qu'il contient des disilicates disodiques cristallins Na2Si2O5 • y H2O où y vaut 0 à 2.
  7. Produit vaisselle selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'il contient des silicates sodiques cristallins à couches qui présentent une teneur de 70 à 100% en poids de bêta-disilicate disodique.
  8. Produit vaisselle selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'il contient des silicates sodiques cristallins à couches qui présentent une teneur de 80 à 100% en poids de delta-disilicate disodique.
  9. Produit vaisselle selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il contient des silicates sodiques cristallins à couches, qui contiennent 1 à 40% en poids d'alpha-disilicate disodique, 0 à 50% en poids de bêta-disilicate disodique, 50 à 98% en poids de delta-disilicate disodique et 0 à 40% en poids de proportions amorphes, en particulier 7 à 21% en poids d'alpha-disilicate disodique, 0 à 12% en poids de bêta-disilicate disodique, 65 à 95% en poids de delta-disilicate disodique et 0 à 20% en poids de proportions amorphes.
  10. Produit vaisselle selon l'une quelconque des revendications 1 ou 3 à 9, caractérisé en ce que le composant a) contient, outre le silicate sodique cristallin à couches de formule (1), en plus des adjuvants choisis parmi l'acide méthylglycinediacétique ou ses sels, le polyphosphate sodique et/ou le citrate sodique.
  11. Produit vaisselle selon l'une quelconque des revendications 1 ou 3 à 10, caractérisé en ce que X représente PF6 -, CH3COO-, Cl-, SO4 2- et en particulier PF6-.
  12. Produit vaisselle selon l'une quelconque des revendications 1 à 11, caractérisé en ce qu'il contient le catalyseur de blanchiment di(hexafluorophosphate) de bis-(N,N',N"-triméthyl-1,4,7-triazacyclononane)-trioxo-dimanganèse (IV) monohydraté.
  13. Composition selon la revendication 1, caractérisée en ce qu'elle est exempte de phosphate.
  14. Produit vaisselle selon l'une quelconque des revendications 1 à 13, caractérisé en ce qu'il contient un ou plusieurs agents de blanchiment choisis dans le groupe constitué par le perborate sodique (monohydraté et tétrahydraté) et le percarbonate sodique.
  15. Produit vaisselle selon l'une quelconque des revendications 1 à 14, caractérisé en ce qu'il contient des alkylènediamines acylées, en particulier la tétraacétyléthylènediamine (TAED), des glycoluriles acylés, en particulier le tétraacétylglycolurile (TAGU), des dérivés triaziniques acylés, en particulier la 1,5-diacétyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), les phénylsulfonates acylés, en particulier le nonanoylsulfonate, l'isononanoylsulfonate ou le lauroyloxybenzènesulfonate (NOBS, ISONOBS ou LOBS) ou leurs dérivés amido, en particulier NACAOBS, des acides hydroxycarboxyliques acylés, en particulier l'acide acétylsalicylique ou l'acide nonanoyloxybenzoïque (NOBA) et l'acide décanoyloxybenzoïque (DOBA).
  16. Produit vaisselle selon la revendication 15, caractérisé en ce qu'il contient des alkylènediamines acylées, en particulier la tétraacétyléthylènediamine (TAED).
  17. Produit vaisselle selon l'une quelconque des revendications 1 à 16, caractérisé en ce qu'il contient du TAED et un des catalyseurs de blanchiment selon la formule (2)
    Figure imgb0013
     dans laquelle a représente 1 ou 2, b représente un nombre de 0 à 4, X représente un anion quelconque monovalent un divalent, de préférence PF6 -, CH3COO-, Cl-, SO4 2- et en particulier PF6 -, et x représente un nombre de 1 à 4, de préférence 1, le TAED et les catalyseurs de blanchiment selon la formule (2) étant de préférence utilisés dans un rapport de mélange de 20:1 à 1:1.
  18. Produit vaisselle selon l'une quelconque des revendications 1 à 17, caractérisé en ce qu'il contient une ou plusieurs enzymes choisies parmi les protéases, les amylases, les mannases, les lipases, les endolases, les pectinases, les cellulases, les pullinases, les cutinases ou les peroxydases.
  19. Produit vaisselle selon l'une quelconque des revendications 1 à 18, caractérisé en ce qu'il contient un compound contenant du silicate sodique cristallin à couches de formule (1) et un composant acide, de préférence un compound contenant du silicate sodique cristallin à couches de formule (1) et des polycarboxylates comme composant acide, de manière particulièrement préférée un compound contenant du silicate sodique cristallin à couches de formule (1) et un homopolymère ou un copolymère non neutralisé ou seulement partiellement neutralisé de l'acide acrylique, de l'acide méthacrylique, de l'acide maléique, du poly(acide aspartique) et/ou d'un acide carboxylique de sucre comme composant acide et en particulier un compound disilicate sodique cristallin à couches/copolymère à base d'acide acrylique/acide maléique.
  20. Procédé pour nettoyer des surfaces comprenant la mise en contact du produit vaisselle selon l'une quelconque des revendications 1 à 19 avec de l'eau et avec la surface à nettoyer, en particulier avec de la vaisselle et des verres, et l'action du liquide de nettoyage aqueux qui s'est formé sur la surface à nettoyer.
  21. Utilisation de la composition selon l'une quelconque des revendications 1 à 19 comme produit vaisselle, en particulier comme produit de lave-vaisselle.
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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015217816A1 (de) 2015-09-17 2017-03-23 Henkel Ag & Co. Kgaa Verwendung hochkonzentrierter Enzymgranulate zur Erhöhung der Lagerstabilität von Enzymen
DE102015014323A1 (de) * 2015-11-05 2017-05-11 Retomax Ag Behandlungsvorrichtung zum Beizen und Phosphatieren von Metallteilen und Behandlungsverfahren sowie Behandlungsanlage zum Beschichten der Metallteile
DE102015014322A1 (de) * 2015-11-05 2017-05-11 Retomax Ag Behandlungsvorrichtung zum Beizen und Phosphatieren von Metallteilen und Behandlungsverfahren sowie Behandlungsanlage zum Verzinken der Metallteile
DE102015014311A1 (de) * 2015-11-05 2017-05-11 Retomax Ag Behandlungsvorrichtung und Behandlungsverfahren mit Verwirbelungseinrichtung zum Beizen und Phosphatieren von Metallteilen
DE102015014304A1 (de) * 2015-11-05 2017-05-11 Retomax Ag Behandlungsvorrichtung zum Beizen und Phosphatieren von Draht oder Drahtteilen und Behandlungsverfahren sowie Behandlungsanlage zum Beschichten des Drahts oder der Drahtteile
DE102015016402A1 (de) * 2015-12-18 2017-06-22 Weylchem Wiesbaden Gmbh Feinteilige Bleichkatalysatoren, Verfahren zu deren Herstellung und deren Verwendung
EP3760699A1 (fr) 2019-07-02 2021-01-06 The Procter & Gamble Company Composition de détergent de lave-vaisselle automatique
EP4008765A1 (fr) * 2020-12-07 2022-06-08 WeylChem Performance Products GmbH Compositions comprenant des composés triazacycliques protonés et agent de blanchiment et agent de nettoyage les contenant

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0530870A1 (fr) 1991-08-23 1993-03-10 Unilever N.V. Composition pour le lavage de la vaisselle en machine
WO1995027773A1 (fr) 1994-04-07 1995-10-19 The Procter & Gamble Company Composition de blanchiment comprenant des activateurs et des catalyseurs de blanchiment
WO1996017921A1 (fr) 1994-12-09 1996-06-13 The Procter & Gamble Company Composition pour le lavage automatique de la vaisselle contenant des particules de peroxydes de diacyle
WO2010022918A1 (fr) 2008-08-30 2010-03-04 Clariant International Ltd. Utilisation d'oxalates de manganèse comme catalyseur de blanchiment

Family Cites Families (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
FR2597473B1 (fr) 1986-01-30 1988-08-12 Roquette Freres Procede d'oxydation de di-, tri-, oligo- et polysaccharides en acides polyhydroxycarboxyliques, catalyseur mis en oeuvre et produits ainsi obtenus.
YU221490A (sh) 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
DE69125309T2 (de) 1990-05-21 1997-07-03 Unilever Nv Bleichmittelaktivierung
JPH06503060A (ja) 1990-12-01 1994-04-07 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン 結晶性二珪酸ナトリウムの水熱製造方法
JP3293636B2 (ja) 1991-01-10 2002-06-17 日本化学工業株式会社 結晶性層状珪酸ナトリウムの製造方法
DE4102743A1 (de) 1991-01-30 1992-08-06 Henkel Kgaa Phosphatfreies reinigungsmittel
JP3299763B2 (ja) 1991-02-14 2002-07-08 日本化学工業株式会社 改質ジ珪酸ナトリウムの製造方法
IT1245063B (it) 1991-04-12 1994-09-13 Ferruzzi Ricerca & Tec Procedimento per l'ossidazione di carboidrati
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
ES2084916T5 (es) 1991-12-29 1999-09-16 Kao Corp Material de intercambio ionico y composicion detergente.
DE4221381C1 (de) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4203923A1 (de) 1992-02-11 1993-08-12 Henkel Kgaa Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
DE4300772C2 (de) 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4303320C2 (de) 1993-02-05 1995-12-21 Degussa Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür
JP2525342B2 (ja) 1993-06-26 1996-08-21 花王株式会社 合成無機ビルダ―及び洗浄剤組成物
DE4417734A1 (de) 1994-05-20 1995-11-23 Degussa Polycarboxylate
ZA956914B (en) 1994-08-19 1997-02-18 Unilever Plc Detergent bleach composition.
AU3077495A (en) 1994-08-19 1996-03-14 Unilever Plc Detergent bleach composition
GB2294705A (en) * 1994-11-05 1996-05-08 Procter & Gamble Bleaching compositions
DE4443177A1 (de) 1994-12-05 1996-06-13 Henkel Kgaa Aktivatormischungen für anorganische Perverbindungen
DE59704543D1 (de) 1996-06-21 2001-10-11 Reckitt Benckiser Nv Mgda-haltige maschinengeschirrspülmittel niederer alkalität
DE19819187A1 (de) * 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
KR100280376B1 (ko) 1998-08-14 2001-02-01 김충섭 결정성 층상 이규산나트륨의 제조방법
DE19854960A1 (de) * 1998-11-29 2000-05-31 Clariant Gmbh Maschinengeschirrspülmittel
DE10102248A1 (de) * 2001-01-19 2002-07-25 Clariant Gmbh Verwendung von Übergangsmetallkomplexen mit Oxim-Liganden als Bleichkatalysatoren
DE10304131A1 (de) 2003-02-03 2004-08-05 Clariant Gmbh Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren
DE10345273A1 (de) 2003-09-30 2005-04-21 Clariant Gmbh Verwendung von Übergangsmetallkomplexen mit Lactamliganden als Bleichkatalysatoren
DE102004003710A1 (de) 2004-01-24 2005-08-11 Clariant Gmbh Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren in Wasch- und Reinigungsmitteln
ES2392347T3 (es) 2005-05-27 2012-12-07 Catexel Limited Proceso de blanqueo
DE102006010670A1 (de) 2006-03-08 2007-09-13 Clariant International Limited Cogranulate
DE102010007059A1 (de) 2010-02-06 2011-08-11 Clariant International Limited Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Metallkomplexen
DE102011010818A1 (de) * 2011-02-10 2012-08-16 Clariant International Ltd. Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren in Wasch- und Reinigungsmitteln

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0530870A1 (fr) 1991-08-23 1993-03-10 Unilever N.V. Composition pour le lavage de la vaisselle en machine
WO1995027773A1 (fr) 1994-04-07 1995-10-19 The Procter & Gamble Company Composition de blanchiment comprenant des activateurs et des catalyseurs de blanchiment
WO1996017921A1 (fr) 1994-12-09 1996-06-13 The Procter & Gamble Company Composition pour le lavage automatique de la vaisselle contenant des particules de peroxydes de diacyle
WO2010022918A1 (fr) 2008-08-30 2010-03-04 Clariant International Ltd. Utilisation d'oxalates de manganèse comme catalyseur de blanchiment

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "Enzymsicherheitsdatenblatt - Termamyl 60 T", NOVOZYMES A/S, 16 March 2001 (2001-03-16), pages 1 - 4
ANONYMOUS: "Savinase ®", NOVO NORDISK A/S, January 1994 (1994-01-01)

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