EP1924676B1 - 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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EP1924676B1
EP1924676B1 EP06793039A EP06793039A EP1924676B1 EP 1924676 B1 EP1924676 B1 EP 1924676B1 EP 06793039 A EP06793039 A EP 06793039A EP 06793039 A EP06793039 A EP 06793039A EP 1924676 B1 EP1924676 B1 EP 1924676B1
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Prior art keywords
acid
mol
weight
diacetic
copolymers
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EP1924676A1 (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.
  • the dishes during the cleaning cycle of the dirt which consists of a variety of food residues, which also contain greasy and oily ingredients, free.
  • the detached dirt particles and components are pumped during further cleaning in the rinse water of the machine. It must be ensured that the detached dirt particles are well dispersed and emulsified, so that they do not settle on the dishes again.
  • 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.
  • Phosphate-free dishwashing detergents containing copolymer are made EP-A-778 340 and EP-A-82564 known.
  • 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.
  • 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 calcium binding capacity and are capable of dispersing the sparingly soluble salts that form from water hardness, and are also capable of dispersing the soil present in the wash liquor. The combination of complexing agents and polycarboxylates thus leads to a particularly good deposit prevention during the automatic dishwashing process.
  • the formulation may be processed as a tablet, powder, gel, capsule, 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.
  • copolymers a) used according to the invention comprise as copolymerized monomer a1) a monoethylenically unsaturated monocarboxylic acid, preferably a C 3 -C 6 -monocarboxylic acid, and / or a water-soluble salt, in particular an alkali metal salt, such as potassium and, above all, sodium salt, or ammonium salt of this acid ,
  • Suitable monomers a1) are: acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. Of course, mixtures of these acids can also be used.
  • Particularly preferred monomer a1) is acrylic acid.
  • the copolymers a) used according to the invention contain from 50 to 99.5 mol% of the monomer a1). If the copolymers are composed only of the monomers a1) and a2), the content of the monomer a1) is generally from 80 to 99.5 mol%, preferably from 90 to 98 mol%. Terpolymers of the monomers a1), a2) and a3) generally contain 60 to 98 mol%, preferably 70 to 95 mol%, of the monomer a1).
  • particularly suitable monomers a2) are the alkoxylation products of the following unsaturated monomers: (meth) allyl alcohol, (meth) allylamines, diallylamines, glycerol monoallyl ethers, trimethylolpropane monoallyl ethers, vinyl ethers, vinylamides and vinylamines.
  • monomers a2) which are based on allyl alcohol, glycerol monoallyl ether, trimethylolpropane monoallyl ether and diallylamine.
  • Very particularly preferred monomers a2) are ethoxylated allyl alcohols which in particular contain from 5 to 20, especially from 10 to 100, moles of EO / mole of allyl alcohol.
  • the monomers a2) can be prepared by well-known standard methods of organic chemistry, for.
  • amidation and transamidation of suitable (meth) acrylic acids by alkoxylation of allyl alcohol, glycerol monoallyl ether, trimethylolpropane monoallyl ether; by etherification of allyl halides with poly-C 2 -C 4 -alkylene oxides and vinylation of polyalkylene oxides with OH or NH end groups with acetylene.
  • copolymers used according to the invention have -SO 3 M or -PO 3 M 2 end groups, these can be introduced by sulfation or phosphation of the monomers (B) or else of the copolymers themselves, for example with chlorosulfonic acid or polyphosphoric acid.
  • the copolymers used according to the invention contain from 0.5 to 20 mol% of the monomer a2). If the copolymers are composed only of the monomers a1) and a2), the content of the monomer a1) is generally from 0.5 to 20 mol%, preferably from 1 to 10 mol%. Terpolymers of the monomers a1), a2) and a3) generally contain from 1 to 15 mol%, preferably from 1 to 10 mol%, of the monomer a2).
  • the copolymers used according to the invention may contain as copolymerized monomer a3) a monoethylenically unsaturated dicarboxylic acid, preferably a C 4 -C 8 dicarboxylic acid.
  • a monoethylenically unsaturated dicarboxylic acid preferably a C 4 -C 8 dicarboxylic acid.
  • an alkali metal salt such as potassium and especially sodium, or ammonium salt are used.
  • Suitable monomers a3) are: maleic acid, fumaric acid, methylenemalonic acid, citraconic acid and itaconic acid. Of course, mixtures of these acids can also be used.
  • Particularly preferred monomer a3) is maleic acid.
  • the monomer a3) is contained in the copolymers used according to the invention, its content is generally from 1 to 30 mol%, preferably from 5 to 30 mol%.
  • the copolymers used according to the invention are preferably composed only of the monomers a1) and a2) or of the monomers a1), a2) and a3).
  • they may also contain another monoethylenically unsaturated monomer a4) which is different from the monomers a1) to a3) but copolymerizable with these monomers.
  • monomers a4) are contained in the copolymers used according to the invention, their content is generally from 1 to 20 mol%, preferably from 1 to 10 mol%. If hydrophobic monomers are used as monomer a4), their content should be selected such that the copolymer retains its hydrophilic character as a whole.
  • the copolymers used according to the invention have an average molecular weight M w of from 30,000 to 500,000 g / mol, preferably from 50,000 to 300,000 g / mol (determined by gel permeation chromatography at room temperature with aqueous eluent).
  • K values are accordingly from 40 to 150, preferably from 50 to 125 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.) H. Fikentscher, Cellulose Chemistry, Vol. 13, pp. 58-64 and 71-74 (1932 )).
  • copolymers used according to the invention can be obtained by the known free-radical polymerization processes.
  • solution and emulsion polymerization should be mentioned, with the solution polymerization is preferred.
  • the polymerization is preferably carried out in water as a solvent.
  • it can also be carried out in alcoholic solvents, in particular in C 1 -C 4 -alcohols, such as methanol, ethanol and isopropanol, or in 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 ° C., in particular from 50 to 120 ° C.
  • suitable thermal initiators are inorganic peroxo compounds and azo compounds. These initiators can be used in combination with reducing compounds as starter / regulator systems.
  • suitable photoinitiators are benzophenone, acetophenone, benzoin ethers, Benzyldialkylketone and derivatives thereof.
  • thermal initiators are used, with inorganic peroxo compounds, in particular hydrogen peroxide and especially sodium peroxodisulfate (sodium persulfate), being preferred.
  • inorganic peroxo compounds in particular hydrogen peroxide and especially sodium peroxodisulfate (sodium persulfate), being preferred.
  • 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.
  • polymerization regulators When polymerization regulators are used, 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 total the monomers.
  • the polymerization temperature is usually at 30 to 200 ° C, preferably at 50 to 150 ° C and particularly preferably at 80 to 130 ° C.
  • the polymerization is preferably carried out under protective gas, such as nitrogen or argon, and may be carried out under atmospheric pressure, but is preferably carried out in a closed system under the evolving autogenous pressure.
  • protective gas such as nitrogen or argon
  • copolymers used according to the invention are usually obtained in the form of a polymer solution which has a solids content of from 10 to 70% by weight, preferably from 25 to 60% by weight.
  • the cleaning formulations according to the invention comprise one or more complexing agents selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, giycin-NN-diacetic acid derivatives, glutamic acid-N, N-diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, S, S-ethylenediamine disuccinic acid and aspartic acid diacetic acid and theirs Salt.
  • Preferred complexing agents b) are methylglycinediacetic acid and / or salts thereof.
  • M is an alkali metal, preferably sodium or potassium, more preferably sodium.
  • 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 (a) 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 (II) may be both random copolymers and block copolymers with 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 An overview of suitable nonionic surfactants give 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 8 -C 18 -alkylbetaines 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 bleaching agents.
  • 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.
  • Oxygen bleaching agents are used in amounts of generally from 0.5 to 30% by weight, preferably from 1 to 20% by weight, particularly preferably from 3 to 15% by weight, based on the total detergent formulation.
  • Chlorine-containing bleaches as well as the combination of chlorine-containing bleaches with peroxide-containing bleaches can also be used.
  • Known chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, N, N'-dichlorobenzoylurea, p-toluenesulfondichloroamide or trichloroethylamine.
  • Preferred chlorine-containing bleaching agents are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate.
  • Chlorine-containing bleaching agents are used in amounts of generally from 0.1 to 20% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.3 to 8% by weight, based on the total detergent formulation ,
  • bleach stabilizers such as, for example, phosphonates, borates, metaborates, metasilicates or magnesium salts, can be added in small amounts.
  • Bleach activators are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or substituted perbenzoic acid.
  • Suitable compounds are those which contain one or more N- or O-acyl groups and / or optionally substituted benzoyl groups, for example substances from the class of the anhydrides, esters, imides, acylated imidazoles or oximes.
  • TAED tetraacetylethylenediamine
  • TAMD tetraacetylmethylenediamine
  • TA-GU tetraacetylglycoluril
  • TAHD tetraacetylhexylenediamine
  • N-acylimides such as N-nonanoylsuccinimide (NOSI)
  • NOSI N-nonanoylsuccinimide
  • acylated phenolsulfonates such as n-nonanoyl or isononanoyloxybenzenesulfonates (n or iso-NOBS)
  • PAG pentaacetylglucose
  • DADHT 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine
  • ISA isatoic anhydride
  • bleach activators are nitrile quats, such as, for example, N-methyl-morpholinium
  • Preferred bleach activators are selected from the group consisting of polyacylated alkylenediamines, more preferably TAED, N-acylimides, more preferably NOSI and acylated phenolsulfonates, more preferably n- or iso-NOBS, MMA and TMAQ.
  • Carboxylic acid anhydrides such as phthalic anhydride
  • acylated polyhydric alcohols such as triacetin, ethylene glycol diacetate or 2,5-diacetoxy-2,5-dihydrofuran
  • DE-A 196 16 693 and DE-A 196 16 767 known enol esters as well as acetylated sorbitol and mannitol and their in EP-A 525 239 described mixtures
  • acylated sugar derivatives in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from the documents WO 94/27 9
  • 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 cleaning agent can be added between 0 and 8 wt .-% of enzymes, based on the total preparation, 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 196 20 267 known N-Ahalogtagen, from 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,
  • TMTACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • Suitable bleach catalysts are preferably bleach-enhancing transition metal complexes or salts from the group consisting of the manganese salts and complexes and the cobalt salts and complexes. Particularly suitable 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 ,
  • one or more alkali carriers may be present.
  • Suitable alkali carriers are ammonium and alkali metal hydroxides, ammonium and alkali metal carbonates, ammonium and alkali metal hydrogencarbonates, ammonium and alkali metal sesquicarbonates, ammonium and alkali metal silicates, ammonium and alkali metal silicates, ammonium and alkali disilicates and mixtures of the abovementioned substances, preference being given to ammonium and alkali metal carbonates and Ammonium and Alkalidisilikate, in particular sodium carbonate, sodium bicarbonate, sodium sesquicarbonate and ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 y H 2 O are used.
  • 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 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.
  • Preferred here are the transition metal salts, which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably from the group of 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 on the items to be washed, in particular made of 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.
  • component (c) it is preferable to use a polyethylene glycol, more preferably having an average molecular weight (weight average molecular weight) of 500 to 30,000 g / mol.
  • 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.
  • nonionic surfactants can be used as component (c). 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 those which are capable of dissolving components (a), (b) and (c).
  • solvents it is possible to use those which are capable of dissolving components (a), (b) and (c).
  • solvents it is possible to use those which are capable of dissolving components (a), (b) and (c).
  • solvents it is possible to use those which are capable of dissolving components (a), (b) and (c).
  • 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 Surface on knife Topping on glasses Covering on plastic 1 6.0 7.5 1.4 2 5.8 7.0 1.4 V1 5.6 6.7 1.4 3 4.4 4.4 1.7 V2 3.5 3.4 1.7 V3 4.1 3.8 1.7

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Claims (4)

  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 99,5 % en moles d'un acide monocarboxylique monoéthyléniquement insaturé et/ou d'un de ses sels,
    a2) 0,5 à 20 % en moles d'un monomère alcoxylé monoéthyléniquement insaturé de formule (I)
    Figure imgb0006
     dans laquelle les variables ont la signification suivants :
    R1 hydrogène ou méthyle ;
    R2 -(CH2)x-O-, -CH2-NR5-, -CH2-O-CH2-CR6R7-CH2-O- ou -CONH- ;
    R3 radicaux alkylène en C2-C4 identiques ou différents, qui peuvent être disposés en blocs ou de manière statistique, la proportion de radicaux éthylène étant d'au moins 50 % en moles ;
    R4 hydrogène, alkyle en C1-C4, -SO3M ou -PO3M2 ;
    R5 hydrogène ou -CH2-CR1=CH2 ;
    R6 -O-[R3-O]n-R4, les radicaux -[R3-O]n- des autres radicaux -[R3-O]n- contenus dans la formule I pouvant être différents ;
    R7 hydrogène ou éthyle ;
    M métal alcalin ou hydrogène ;
    n 4 à 250 ;
    x 0 ou 1,
    a3) 0 à 50 % en moles d'un acide dicarboxylique monoéthyléniquement insaturé, un de ses anhydrides et/ou un de ses sels,
    a4) 0 à 20 % en moles d'un monomère copolymérisable monoéthyléniquement insaturé supplémentaire,
    le copolymère présentant un poids moléculaire moyen Mw de 30 000 à 500 000 g/mol et une valeur K de 40 à 150, mesurée à une valeur de pH de 7 dans une solution aqueuse à 1 % en poids à 25 °C,
    b) 1 à 50 % en poids d'agents complexants, choisis dans le groupe constitué de l'acide nitrilotriacétique, l'acide éthylène diamine tétraacétique, l'acide diéthylène triamine pentaacétique, l'acide hydroxyéthyléthylène diamine triacétique et l'acide glycine-N,N-diacétique et ses dérivés, l'acide glutamique-N,N-diacétique, l'iminodisuccinate, l'hydroxyiminodisuccinate, le S,S-éthylène diamine disuccinate et l'acide asparaginique-diacétique, ainsi que les sels des substances susmentionnées,
    c) 1 à 15 % en poids de tensioactifs non ioniques faiblement moussants,
    d) 0,1 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) 30 à 95 % en poids des copolymères selon la revendication 1 contenant les composants a1), a2) et éventuellement a3) et a4),
    b) 5 à 70 % en poids d'agents complexants, choisis dans le groupe constitué de l'acide nitrilotriacétique, l'acide éthylène diamine tétraacétique et les dérivés de l'acide glycine-N,N-diacétique, l'acide glutamique-N,N-diacétique, l'acide iminodisuccinique, l'acide hydroxyiminodisuccinique, l'acide S,S-éthylène diamine disuccinique et l'acide asparaginique-diacétique, ainsi que les sels des acides susmentionnés,
    c) 0 à 20 % en poids d'un polyéthylène glycol, d'un tensioactif non ionique ou d'un de leurs mélanges.
  4. Utilisation d'une combinaison de copolymères selon la revendication 1 contenant les composants a1), a2) et éventuellement a3) et a4) et d'agents complexants b), choisis dans le groupe constitué de l'acide nitriloacétique, l'acide éthylène diamine tétraacétique et les dérivés de l'acide glycine-N,N-diacétique, l'acide glutamique-N,N-diacétique, l'acide iminodisuccinique, l'acide hydroxyiminodisuccinique, l'acide S,S-éthylène diamine disuccinique et l'acide asparaginique-diacétique, ainsi que les sels des acides susmentionnés, en tant qu'additif anti-tartre dans des formulations de lavage pour le lavage de la vaisselle en machine.
EP06793039A 2005-08-31 2006-08-29 Preparations detergentes pour lavage en lave-vaisselle contenant des polycarboxylates a modification hydrophile Not-in-force EP1924676B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005041349A DE102005041349A1 (de) 2005-08-31 2005-08-31 Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
PCT/EP2006/065751 WO2007025955A1 (fr) 2005-08-31 2006-08-29 Preparations detergentes pour lavage en lave-vaisselle contenant des polycarboxylates a modification hydrophile

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EP1924676A1 EP1924676A1 (fr) 2008-05-28
EP1924676B1 true EP1924676B1 (fr) 2009-04-15

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AT (1) ATE428765T1 (fr)
BR (1) BRPI0615333A2 (fr)
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DE (2) DE102005041349A1 (fr)
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CA2620475C (fr) 2014-11-18
CN101300334A (zh) 2008-11-05
ES2324239T3 (es) 2009-08-03
US20120010117A1 (en) 2012-01-12
JP5345394B2 (ja) 2013-11-20
JP2009506184A (ja) 2009-02-12
WO2007025955A1 (fr) 2007-03-08
CN101300334B (zh) 2012-05-16
ATE428765T1 (de) 2009-05-15
DE502006003477D1 (de) 2009-05-28
US20120196784A1 (en) 2012-08-02
US20100249010A1 (en) 2010-09-30
KR101363124B1 (ko) 2014-02-13
CA2620475A1 (fr) 2007-03-08
US20100227787A1 (en) 2010-09-09
US8093196B2 (en) 2012-01-10
EP1924676A1 (fr) 2008-05-28
KR20080041274A (ko) 2008-05-09
BRPI0615333A2 (pt) 2012-12-11
DE102005041349A1 (de) 2007-03-01

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