EP1924675B2 - Preparations detergentes pour lavage en lave-vaisselle contenant des polycarboxylates a modification hydrophile - Google Patents

Preparations detergentes pour lavage en lave-vaisselle contenant des polycarboxylates a modification hydrophile Download PDF

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EP1924675B2
EP1924675B2 EP06778368.8A EP06778368A EP1924675B2 EP 1924675 B2 EP1924675 B2 EP 1924675B2 EP 06778368 A EP06778368 A EP 06778368A EP 1924675 B2 EP1924675 B2 EP 1924675B2
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Prior art keywords
acid
weight
mol
copolymer
water
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EP1924675A1 (fr
EP1924675B1 (fr
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Tanja Seebeck
Jürgen Tropsch
Lars Kissau
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the invention relates to cleaning formulations for machine dishwashing.
  • phosphate-based Many of the formulations on the market are phosphate-based.
  • the phosphate used is ideal for use as it combines many of the useful properties required in machine dishwashing.
  • phosphate is able to disperse water hardness (i.e., insoluble salts of water hardness causing ions such as calcium and magnesium ions). This task is still achieved via the ion exchanger of the machines.
  • water hardness i.e., insoluble salts of water hardness causing ions such as calcium and magnesium ions
  • This task is still achieved via the ion exchanger of the machines.
  • a large proportion of dishwashing products today are offered in the form of so-called 3-in-1 formulations, in which the function of the ion exchanger is no longer necessary.
  • the phosphate usually takes over the softening of the water in combination with phosphonates. Furthermore, the phosphate disperses the detached dirt and thus prevents re-deposition of the dirt on the dishes.
  • the object of the invention is to provide phosphate-free cleaning formulations for machine dishwashing.
  • the object of the invention is, in particular, to provide such formulations which, without the use of additional rinse aid, result in a dish-free, covering-free and drip-free dish.
  • WO-A-2005042684 discloses dishwashing detergents containing hydrophilically modified polycarboxylate polymers.
  • EP-A-778 340 discloses phosphate-free dishwashing detergents having a rinse-aid function, comprising copolymers of acrylic acid and alkylene oxide adducts of the allyl alcohol.
  • US-A-6172036 discloses rinse aid containing methylglycinediacetic acid and acrylic-methacrylic acid polymers.
  • the complexing agent takes on the task of complexing the water hardness causing ions (calcium and magnesium ions) contained in the rinse water or in the food residues.
  • Polycarboxylates also have a calcium binding capacity and are also able to disperse the water-hard-forming sparingly soluble salts and the dirt present in the wash liquor. It is surprising that MGDA and GLDA in combination with the hydrophilically modified polycarboxylates have a better deposit-inhibiting effect than EDTA, although their complexation constant for Ca ions is smaller than that of EDTA.
  • the formulation can be made into tablets, powders, gel, capsules, extrudate or solution. These may be formulations for both household and commercial applications.
  • the object is further achieved by the use of a combination of copolymers a) and complexing agents b) as a builder system in cleaning formulations for machine dishwashing.
  • the builder system takes on the task of complexing the water hardness-causing ions (calcium and magnesium ions) contained in the rinse water or in the food residues.
  • the object is further achieved by the use of a combination of copolymers a) and complexing agents b) as a deposit-inhibiting additive in cleaning formulations for machine dishwashing.
  • the alkylene oxide units containing copolymers a) contain as copolymerized components a1) and a2) acrylic acid or methacrylic acid and / or water-soluble salts of these acids, in particular the alkali metal salts, such as potassium and especially sodium salts, and ammonium salts.
  • the proportion of acrylic acid a1) in the copolymers to be used according to the invention is 50 to 93 mol%, preferably 65 to 85 mol% and particularly preferably 65 to 75 mol%.
  • Methacrylic acid a2) is contained in the copolymers to be used according to the invention to 5 to 30 mol%, preferably 10 to 25 mol% and especially to 15 to 25 mol%.
  • Particularly suitable examples of the monomers (I) are: methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, Ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, with methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate being preferred and methoxypolyethylene glycol methacrylate being particularly preferred.
  • the polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.
  • the proportion of nonionic monomers a3) in the copolymers to be used according to the invention is 2 to 20 mol%, preferably 5 to 15 mol% and especially 5 to 10 mol%.
  • the copolymers to be used according to the invention generally have an average molecular weight M w of from 3,000 to 50,000, preferably from 10,000 to 30,000 and more preferably from 15,000 to 25,000.
  • the K value of the copolymers is usually from 15 to 40, in particular from 20 to 35, especially from 27 to 30 (measured in 1 wt .-% aqueous solution at 25 ° C, according to H. Fikentscher, cellulose chemistry, Vol. 13, pp. 58-64 and 71-74 (1932)).
  • copolymers to be used according to the invention can be prepared by free-radical polymerization of the monomers. It can be worked by all known radical polymerization. In addition to the bulk polymerization, the methods of solution polymerization and emulsion polymerization should be mentioned in particular, with the solution polymerization being preferred.
  • the polymerization is preferably carried out in water as a solvent.
  • alcoholic solvents in particular C 1 -C 4 -alcohols, such as methanol, ethanol and isopropanol, or mixtures of these solvents with water.
  • Suitable polymerization initiators are both thermally and photochemically (photoinitiators) decomposing and thereby radical-forming compounds.
  • thermally activatable polymerization initiators preference is given to initiators having a decomposition temperature in the range from 20 to 180.degree. C., in particular from 50 to 90.degree.
  • suitable thermal initiators are inorganic peroxo compounds and azo compounds. These initiators can be used in combination with reducing compounds as starter / regulator systems.
  • polymerization regulators can also be used. Suitable compounds known to those skilled in the art, e.g. Sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecylmercaptan.
  • Sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecylmercaptan.
  • their amount used is usually 0.1 to 15 wt .-%, preferably 0.1 to 5 wt .-% and particularly preferably 0.1 to 2.5 wt .-%, based on the monomers a1), a2) and a3).
  • the polymerization temperature is usually at 30 to 200 ° C, preferably at 50 to 150 ° C and particularly preferably at 80 to 120 ° C.
  • the polymerization may be carried out under atmospheric pressure, but preferably it is carried out in the closed system under the evolving autogenous pressure.
  • the monomers a1), a2) and a3) can be used as such, but it is also possible to use reaction mixtures which are obtained in the preparation of the monomers a3).
  • reaction mixtures which are obtained in the preparation of the monomers a3).
  • the monomer mixture obtained in the esterification of polyethylene glycol monomethyl ether with an excess of methacrylic acid can be used.
  • the esterification can also be carried out in situ in the polymerization mixture by (1) combining acrylic acid, (2) a mixture of methacrylic acid and polyethylene glycol monomethyl ether and (3) free radical initiator in parallel.
  • a catalyst necessary for the esterification such as methanesulfonic acid or p-toluenesulfonic acid, may additionally be used.
  • copolymers used according to the invention a) can also by polymer-analogous reaction, for example by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol monoalkyl ether.
  • polyalkylene glycol monoalkyl ether preferred is the radical copolymerization of the monomers.
  • the cleaning formulations according to the invention contain one or more complexing agents which are selected from the group consisting of glycine-N, N-diacetic acid derivatives, glutamic acid-N, N-diacetic acid and salts thereof.
  • Preferred complexing agents b) are methylglycinediacetic acid and glutamic acid diacetic acid, particularly preferred complexing agents b) are methylglycinediacetic acid or its salts.
  • R is a C 1-12 -alkyl radical, preferably a C 1-6 -alkyl radical, more preferably a methyl or ethyl radical.
  • Particularly preferred component (b) used is an alkali metal salt of methylglycinediacetic acid (MGDA). Most preferably, the trisodium salt of methylglycinediacetic acid is used.
  • the cleaning formulations according to the invention contain weakly or low-foaming nonionic surfactants. These are generally present in proportions of 1 to 15 wt .-%, preferably 1 to 10 wt .-%.
  • the surfactants of formula (III) may be both random copolymers and block copolymers having one or more blocks.
  • di- and multiblock copolymers composed of ethylene oxide and propylene oxide are used, for example, under the name Pluronic ® (BASF Aktiengesellschaft) or Tetronic ® (BASF Corporation) are commercially available.
  • Pluronic ® BASF Aktiengesellschaft
  • Tetronic ® BASF Corporation
  • reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can be used.
  • amine oxides or alkyl glycosides are also suitable.
  • suitable nonionic surfactants are the EP-A 851 023 as well as the DE-A 198 19 187 ,
  • the formulations may further contain anionic, cationic, amphoteric or zwitterionic surfactants, preferably in admixture with nonionic surfactants.
  • Suitable anionic and zwitterionic surfactants are also in EP-A 851 023 such as DE-A 198 19 187 called.
  • Suitable cationic surfactants are, for example, C 8 -C 16 -dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with a long-chain alkyl radical.
  • Suitable amphoteric surfactants are, for example, derivatives of secondary or tertiary amines such as C 6 -C 18 -alkyl betaines or C 6 -C 15 -alkylsulfobetaines or amine oxides such as alkyldimethylamine oxides.
  • the cleaning formulations according to the invention may contain bleaches and optionally bleach activators.
  • Bleaching agents are subdivided into oxygen bleaching agents and chlorine-containing bleaches. Use as oxygen bleach find alkali metal perborates and their hydrates and alkali metal percarbonates. Preferred bleaching agents here are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate.
  • oxygen bleaching agents are persulfates and hydrogen peroxide.
  • Typical oxygen bleaches are also organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.
  • organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.
  • Bleach activators are used in amounts of generally from 0.1 to 10% by weight, preferably from 1 to 9% by weight, particularly preferably from 1.5 to 8% by weight, based on the total detergent formulation.
  • the cleaning formulations of the invention may contain further builders. It is possible to use water-soluble and water-insoluble builders whose main task is the binding of calcium and magnesium.
  • the cleaning formulations according to the invention comprise one or more enzymes.
  • the detergent can be added between 0 and 8 wt .-% of enzymes based on the total preparation in order to increase the performance of the detergents or to ensure under mild conditions, the cleaning performance of the same quality.
  • the most commonly used enzymes include lipases, amylases, cellulases and proteases.
  • esterases, pectinases, lactases and peroxidases can be used.
  • the cleaning agents according to the invention may contain, as component g), further additives such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents and water.
  • further additives such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents and water.
  • EP-A 446 982 and EP-A 453 003 be known Sulfonimine and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts in the inventive cleaning formulations.
  • transition metal compounds include those of DE-A 195 29 905 known manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their DE-A 19620267 known N-analogues consisting of DE-A 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in DE-A 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which DE-A 196 20 411 known cobalt, iron, copper and ruthenium-amine complexes which are known in DE-A 44 16 438 described manganese, copper and cobalt complexes, which in EP-A 272 030 described cobalt complexes consisting of EP-A 693 550 known manganese complexes that are made EP-A 392 592 known manganese, iron,
  • Binuclear manganese complexes containing 1,4,7-trimethyl-1,4,7-triazacyclononane (TMTACN) such as, for example, [(TMTACN) 2 Mn IV Mn IV ( ⁇ -O) 3 ] 2+ (PF 6 - ) 2 are also useful as effective bleach catalysts. These manganese complexes are also described in the aforementioned publications.
  • Bleach catalysts which are preferred are bleach-enhancing transition metal complexes or salts from the group consisting of the manganese salts and complexes and the cobalt salts and complexes.
  • the cobalt (amine) complexes Especially preferred are the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate or [(TMTACN) 2 Mn IV Mn IV ( ⁇ -O) 3 ] 2+ (PF 6 - ) 2 .
  • Bleach catalysts can be used in amounts of from 0.0001 to 5% by weight, preferably from 0.0025 to 1% by weight, particularly preferably from 0.01 to 0.25% by weight, based on the total detergent formulation ,
  • alkali carriers may be present.
  • Suitable alkali carriers are ammonium and / or alkali metal hydroxides, ammonium and / or alkali metal carbonates, ammonium and / or alkali metal hydrogencarbonates, ammonium and / or alkali metal sesquicarbonates, ammonium and / or alkali metal silicates, ammonium and / or alkali disilicates, ammonium and / or Alkali metal silicates and mixtures of the aforementioned substances, preference being given to using ammonium and / or alkali metal carbonates and ammonium and / or alkali disilicates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate and ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O.
  • silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • active chlorine-containing agents are often used in cleaner formulations, which can significantly reduce the corrosion of the silver surface.
  • oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g.
  • Salts and complex inorganic compounds such as salts of the metals Mn, Ti, Zr Hf, V, Co and Ce are often used.
  • the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably from the group of the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl ) Complexes, the chlorides of cobalt or manganese and of manganese sulfate.
  • zinc compounds or bismuth compounds can be used to prevent corrosion of the items to be washed, in particular glass.
  • Paraffin oils and silicone oils can optionally be used as defoamers and for the protection of plastic and metal surfaces. Defoamers are generally used in proportions of 0.001 wt .-% to 5 wt .-%.
  • dyes such as patent blue, preservatives such as Kathon CG, perfumes and other perfumes may be added to the cleaning formulation of the invention.
  • a suitable filler is, for example, sodium sulfate.
  • a polyethylene glycol more preferably having an average molecular weight (weight average molecular weight) of 500 to 30,000 g / mol can be used.
  • the polyethylene glycol used as component c) preferably has OH end groups and / or C 1-6 -alkyl end groups. Particular preference is given to using in the mixture according to the invention as component c) a polyethylene glycol which has OH and / or methyl end groups.
  • the polyethylene glycol has a molecular weight (weight average molecular weight) of 1000 to 5000 g / mol, most preferably from 1200 to 2000 g / mol.
  • Suitable compounds may be used as component c) nonionic surfactants. These are preferably selected from the group consisting of alkoxylated primary alcohols, alkoxylated fatty alcohols, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides and polyhydroxy fatty acid amides.
  • 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 may contain linear and branched radicals in the mixture, 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 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols containing 3 EO, 4 EO or 7 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 12-14 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means that may be a whole or fractional number for a particular product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution ("narrow range ethoxylates", NRE).
  • the preparation of the mixed powders or mixed granules according to the invention is carried out by mixing the components a), b) and c) as a powder, heating the mixture and adjusting the powder properties in the subsequent cooling and shaping process.
  • the mixed powders or mixed granules according to the invention can also be prepared by dissolving the components a), b) and c) in a solvent and spray-drying the resulting mixture, wherein a granulation step can follow.
  • the components a) to c) can be dissolved separately, wherein the solutions are subsequently mixed, or a powder mixture of the components can be dissolved in water.
  • solvents it is possible to use all those which can dissolve components a), b) and c); preference is given, for example, to using alcohols and / or water, more preferably water.
  • Copolymer The preparation of the copolymer (component a)) was carried out according to Example 1 of DE-A 102 25 594 as follows:
  • Dishwasher Miele G 686 SC rinses: 2 rinses 55 ° C normal (without pre-rinse) ware: Messer (WMF table knife Berlin, Monoblock) and Fassformglasbecher (Matador, Ruhr crystal), plastic plate (SAN plate Kayser); Ballast dishes: 6 dessert plates black Rinse temperature: 65 ° C Water hardness: 14 ° dH (corresponding to 250 mg CaCO 3 / kg) or 25 ° dH (corresponding to 445 mg CaCO 3 / kg)
  • Table 2 shows the test conditions of Examples 1 to 6 and Comparative Examples V1 and V9: Table 2: example formulation Water hardness [° dH] dirt polymer 1 1 25 without Copolymer from DE 102 25 594 V1 1 25 without without V2 6 25 without Copolymer off DE 102 25 594 2 2 25 without Copolymer off DE 102 25 594 V3 2 25 without without 3 1 25 With Copolymer off DE 102 25 594 V4 1 25 With without V5 6 25 With Copolymer off DE 102 25 594 4 1 14 without Copolymer off DE 102 25 594 V6 1 14 without without 5 3 25 without Copolymer off DE 102 25 594 V7 3 25 without Polyacrylic acid sodium salt (Mw 8000) V8 5 25 without Copolymer off DE 102 25 594 6 4 25 without Copolymer off DE 102 25 594 V9 4 25 without Polyacrylic acid sodium salt (Mw 8000)
  • the washware was evaluated 18 hours after cleaning by visual inspection in a black painted light box with halogen spot and pinhole using a grading scale from 10 (very good) to 1 (very bad).
  • the highest grade of 10 corresponds to surface and drip-free surfaces, from grades ⁇ 3 on, coverings and drops are already recognizable under normal room lighting, so they are perceived as disturbing.
  • Table 3 Rating (grade) example knife glasses plastic 1 5.3 4.5 1.7 V1 1 1.25 1.7 V2 1.1 4.0 1.7 2 4.3 4.2 1.7 V3 1 1 1.7 3 5.5 4.4 1.7 V4 2.2 1.5 3.3 V5 1.8 3.2 1.7 4 6 5.8 1.7 V6 1 3.4 4.2 5 7.5 7 1.7 V7 5 5 1.7 V8 6.9 3.2 3.3 6 4.5 6.9 1.7 V9 5.1 3.7 1.7 1.7

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Claims (3)

  1. Formulation de lavage sans phosphates pour le lavage de la vaisselle en machine, contenant en tant que composants :
    a) 1 à 20 % en poids de copolymères de
    a1) 50 à 93 % en moles de l'acide acrylique et/ou d'un des sels de l'acide acrylique qui sont solubles dans l'eau,
    a2) 5 à 30 % en moles de l'acide méthacrylique et/ou d'un des sels de l'acide méthacrylique qui sont solubles dans l'eau
    et
    a3) 2 à 20 % en moles d'au moins un monomère non ionique de formule (I)
    Figure imgb0006
     dans laquelle les variables ont la signification suivante :
    R1 hydrogène ou méthyle ;
    R2 une liaison chimique ou alkylène en C1-C6 ramifié ou non;
    R3 radicaux alkylène en C2-C4 identiques ou différents, ramifiés ou non;
    R4 alkyle en C1-C6 ramifié ou non ;
    n 3 à 50,
    les monomères a1) à a3) étant incorporés par polymérisation de manière statique ou en blocs,
    b) 1 à 50 % en poids d'agents complexants, choisis dans le groupe constitué des dérivés de l'acide glycine-N,N-diacétique et l'acide glutamique-N,N-diacétique, et leurs sels,
    c) 1 à 15 % en poids de tensioactifs non ioniques faiblement moussants,
    d) 0 à 30 % en poids d'agents blanchissants et éventuellement d'activateurs de blanchiment,
    e) 0 à 60 % en poids d'adjuvants supplémentaires,
    f) 0 à 8 % en poids d'enzymes,
    g) 0 à 50 % en poids d'un ou de plusieurs additifs supplémentaires tels que des tensioactifs anioniques ou zwitterioniques, des catalyseurs de blanchiment, des porteurs d'alcalis, des inhibiteurs de corrosion, des agents antimousses, des colorants, des parfums, des charges, des solvants organiques et de l'eau,
    la somme des composants a) à g) représentant 100 % en poids.
  2. Formulation de lavage sans phosphates selon la revendication 1, caractérisée en ce que l'agent complexant b) est l'acide méthylglycine-diacétique et/ou ses sels.
  3. Poudres mixtes ou granulats mixtes pour une utilisation dans des formulations de lavage pour le lavage de la vaisselle en machine, à base de
    a) 10 à 95 % en poids des copolymères selon la revendication 1 contenant les composants a1), a2) et a3),
    b) 5 à 80 % en poids d'agents complexants, choisis dans le groupe constitué des dérivés de l'acide glycine-N,N-diacétique et l'acide glutamique-N,N-diacétique et leurs sels,
    c) 0 à 20 % en poids d'un polyéthylène glycol, d'un tensioactif non ionique ou d'un de leurs mélanges.
EP06778368.8A 2005-08-31 2006-08-28 Preparations detergentes pour lavage en lave-vaisselle contenant des polycarboxylates a modification hydrophile Not-in-force EP1924675B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005041347A DE102005041347A1 (de) 2005-08-31 2005-08-31 Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
PCT/EP2006/065711 WO2007025944A1 (fr) 2005-08-31 2006-08-28 Preparations detergentes pour lavage en lave-vaisselle contenant des polycarboxylates a modification hydrophile

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Publication Number Publication Date
EP1924675A1 EP1924675A1 (fr) 2008-05-28
EP1924675B1 EP1924675B1 (fr) 2010-11-10
EP1924675B2 true EP1924675B2 (fr) 2015-07-29

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US (2) US8193139B2 (fr)
EP (1) EP1924675B2 (fr)
JP (1) JP2009506183A (fr)
KR (1) KR101363153B1 (fr)
CN (1) CN101253257A (fr)
AT (1) ATE487783T1 (fr)
BR (1) BRPI0614939A2 (fr)
CA (1) CA2620240C (fr)
DE (2) DE102005041347A1 (fr)
ES (1) ES2355523T5 (fr)
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KR20080041217A (ko) 2008-05-09
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JP2009506183A (ja) 2009-02-12
ATE487783T1 (de) 2010-11-15
US8193139B2 (en) 2012-06-05
US20120122748A1 (en) 2012-05-17
EP1924675A1 (fr) 2008-05-28
DE502006008293D1 (de) 2010-12-23
CA2620240C (fr) 2014-04-01
BRPI0614939A2 (pt) 2013-01-01
ES2355523T3 (es) 2011-03-28
ES2355523T5 (es) 2015-09-21
KR101363153B1 (ko) 2014-02-13
US8440601B2 (en) 2013-05-14
WO2007025944A1 (fr) 2007-03-08
US20100160203A1 (en) 2010-06-24
EP1924675B1 (fr) 2010-11-10
DE102005041347A1 (de) 2007-03-01

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