EP1924675A1 - 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

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Publication number
EP1924675A1
EP1924675A1 EP06778368A EP06778368A EP1924675A1 EP 1924675 A1 EP1924675 A1 EP 1924675A1 EP 06778368 A EP06778368 A EP 06778368A EP 06778368 A EP06778368 A EP 06778368A EP 1924675 A1 EP1924675 A1 EP 1924675A1
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Prior art keywords
acid
weight
mol
salts
water
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EP06778368A
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German (de)
English (en)
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EP1924675B2 (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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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
    • C11D3/16—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.
  • DE 102 25 594 A1 describes the use of copolymers comprising alkylene oxide units in detergents and cleaners and also washing and cleaning compositions containing these copolymers. However, no combinations of these polymers with complexing agents are described.
  • the complexing agent takes on the task of complexing the water hardness-causing ions (calcium and magnesium ions) contained in the rinsing 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.
  • phosphate-free cleaning formulations for machine dishwashing containing as components:
  • Acrylic acid a2) 5 to 30 mol% of methacrylic acid and / or a water-soluble salt of
  • R 1 is hydrogen or methyl
  • R 2 is a chemical bond or unbranched or branched CrC 6 -
  • Alkylene radicals, R 4 unbranched or branched C 1 -C 6 -alkyl, n 3 to 50,
  • the monomers a1) to a3) being copolymerized randomly or in blocks,
  • additional substances such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents and Water
  • 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%.
  • copolymers contain as component a3) nonionic monomers of the formula (I)
  • R 1 is hydrogen or preferably methyl
  • RR 22 unbranched or branched CrC 6 alkylene or, preferably, a chemical
  • R 3 identical or different unbranched or branched C 2 -C 4 -alkylene radicals, especially C 2 -C 3 -alkylene radicals, in particular ethylene,
  • R 4 is unbranched or branched C 1 -C 6 -alkyl, preferably C 1 -C 2 -alkyl,
  • n is 3 to 50, preferably 5 to 40, particularly preferably 10 to 30.
  • 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, ethylene xypolyethylene 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 is 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. In this case, it is possible to work according to all known radical polymerization processes. 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.
  • it can also be used in alcoholic solvents, in particular C 1 -C 4 -alcohols, such as Methanol, ethanol and isopropanol, or mixtures of these solvents are made 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 combining (1) acrylic acid, (2) a mixture of methacrylic acid and polyethylene glycol monomethyl ether and (3) radical initiator in parallel.
  • a catalyst necessary for the esterification such as methanesulfonic acid or p-toluenesulfonic acid, may additionally be used.
  • the copolymers a) used according to the invention can also be prepared by a polymer-analogous reaction, for example by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol monoalkyl ether. However, 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.
  • Preferred glycine-N, N-diacetic acid derivatives are those described in EP-A 0 845 456. Suitable glycine-N, N-diacetic acid derivatives are accordingly compounds of the general formula (II)
  • M alkali metal preferably sodium or potassium, more preferably sodium
  • R is a Ci- 12 alkyl group, preferably a Ci -6 alkyl group, more preferably methyl or ethyl.
  • 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 .-%.
  • Suitable nonionic surfactants include the surfactants of the general formula (III) R 1 - (OCH 2 CHR 2 ) P (OCH 2 CHR 3 ) m -OR 4 (III)
  • R 1 is a linear or branched alkyl radical having 6 to 24 C atoms
  • R 2 and R 3 independently of one another are hydrogen or a linear or branched alkyl radical having 1-16 C atoms, where R 2 ⁇ R 3 and R 4 is a linear or branched alkyl radical having 1 to 8 C atoms,
  • p and m are independently 0 to 300.
  • the surfactants of formula (IM) may be both random copolymers and block copolymers with one or more blocks.
  • the formulations may further contain anionic, cationic, amphoteric or zwitterionic surfactants, preferably in admixture with nonionic surfactants.
  • anionic and zwitterionic surfactants are also mentioned in EP-A 851 023 and DE-A 198 19 187.
  • 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 8 -alkylbetaines or C 6 -C 5 -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.
  • Also usable as 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-diperoxazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutan-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-diperoxazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutan-1,4-diacid.
  • oxygen bleaches can also be used in the detergent formulation:
  • 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-Chlorosulfamid, chloramine T, dichloramine T, chloramine B, N, N '-Dichlorbenzoylharnstoff, p-toluene- or sulfondichloramid Trichlorethylamin.
  • 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 phosphonates, borates, metaborates, metasilicates or magnesium salts can be added in small amounts.
  • Bleach activators are compounds which are aliphatic under perhydrolysis conditions
  • Peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to
  • Suitable compounds are one or more N- or O-acyl groups and / or optionally Substituted benzoyl groups, for example, substances from the class of anhydrides, esters, imides, acylated imidazoles or oximes.
  • TAED tetraacetylethylenediamine
  • TAMD tetraacetylmethylenediamine
  • TAGU tetraacetylglycoluril
  • TAHD tetraacetylhexylenediamine
  • N-acylimides such as N-nonanoylsuccinimide (NOSI)
  • NOSI N-nonanoylsuccinimide
  • acylated phenolsulphonates for example n-nonanoyl or isononanoyloxybenzenesulphonates (n- or iso-NOBS)
  • PAG pentaacetylglucose
  • DADHT 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine
  • ISA isoic anhydride
  • nitrile quats such as N-methyl morpholinium acetonitrile salts (MMA salts) or trimethyl ammonium acetonitrile salts (TMAQ salts).
  • MMA salts N-methyl morpholinium acetonitrile salts
  • TMAQ salts trimethyl ammonium acetonitrile salts
  • Preferred bleach activators are selected from the group consisting of polyacylated alkylenediamines, more preferably TAED, N-acylimides, particularly preferably NO-Sl, 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; the enol esters known from DE-A 196 16 693 and DE-A 196 16 767 and also acetylated sorbitol and mannitol or their mixtures described in EP-A 525 239; acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and also acetylated, optionally N-alkylated, glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are described in WO 94/27970 ,
  • hydrophilic substituted acyl acetals listed in DE-A 196 16 769 and the acyl lactams described in DE-A 196 16 770 and WO 95/14 075 can be used as well as the known from DE-A 44 43 177 combinations of conventional bleach activators.
  • 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.
  • carboxylic acids and their salts such as alkali citrates, in particular anhydrous trisodium citrate or trisodium citrate dihydrate, alkali metal succinates, alkali metalates, fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate, .alpha.-hydroxypropionic acid;
  • polycarboxylic acids and their salts such as polyacrylic acid, polymethacrylic acid, copolymers of maleic acid and acrylic acid;
  • Phosphonates such as 2-phosphono-1, 2,4-butanetricarboxylic acid, aminotri- (methylenephosphonic acid), 1-hydroxyethylene (1,1-diphosphonic acid), ethylenediamine tetramethylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid or diethylene triamine pentamethylene phosphonic acid;
  • Silicates such as sodium disilicate and sodium metasilicate
  • water-insoluble builders such as zeolites and crystalline phyllosilicates.
  • 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. toren, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents and water.
  • further additives such as anionic or zwitterionic surfactants, bleach catalysts. toren, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents and water.
  • the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from EP-A 446 982 and EP-A 453 003 can also be present as so-called bleach catalysts in the inventive cleaning formulations.
  • Suitable transition metal compounds include, for example, the manganese, iron, cobalt, ruthenium or molybdenum salt complexes known from DE-A 195 29 905 and their N-analog compounds known from DE-A 196 20 267, US Pat.
  • Binuclear manganese complexes containing 1, 4,7-trimethyl-1, 4,7-triazacyclononane (TMTACN) such as [(TMTACN) 2 Mn lv Mn lv ( ⁇ -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. Particularly 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 lv Mn lv ( ⁇ -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 , As further constituents of the cleaner 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 metasilicates and mixtures of the aforementioned substances, preferably ammonium and / or Alkalicar- carbonates and ammonium and / or alkali metal disilicates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate and SS and ⁇ -sodium Na 2 Si 2 O S yH 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 / 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.
  • Preferred here are 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.
  • the present invention also provides mixed powders or mixed granules for use in cleaning formulations for machine dishwashing a) from 10 to 95% by weight of the copolymers of components a1), a2) and optionally a3) and a4), as defined above,
  • 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 Ci -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 residue is linear or preferably methyl-branched in the 2-position may contain linear or branched radicals in the mixture, as they are usually present in Oxoal- koholresten.
  • 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.
  • Preferred ethoxylated alcohols include, for example, C 2 - 14 alcohols containing 3 EO, 4 EO or 7 EO, n-alcohols containing 7 EO, C 3- I 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 - 1 8-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -i 4 -alcohol with 3 EO and Ci 2 -i 4 -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 rank 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, particularly 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:
  • Rinses 2 rinses 55 ° C Normal (without pre-rinse)
  • Washware Knife (WMF table knife Berlin, Monoblock) and keg-shaped glass beaker (Matador, Ruhr Kristall), plastic dish (SAN dish Kayser); Ballast dishes: 6 dessert plates black rinse temperature: 65 ° 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.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
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

Publications (3)

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

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US (2) US8193139B2 (fr)
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KR (1) KR101363153B1 (fr)
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AT (1) ATE487783T1 (fr)
BR (1) BRPI0614939A2 (fr)
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DE (2) DE102005041347A1 (fr)
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CA2620240A1 (fr) 2007-03-08
US20120122748A1 (en) 2012-05-17
ATE487783T1 (de) 2010-11-15
CA2620240C (fr) 2014-04-01
ES2355523T3 (es) 2011-03-28
KR20080041217A (ko) 2008-05-09
US8193139B2 (en) 2012-06-05
DE102005041347A1 (de) 2007-03-01
CN101253257A (zh) 2008-08-27
EP1924675B2 (fr) 2015-07-29
US20100160203A1 (en) 2010-06-24
EP1924675B1 (fr) 2010-11-10
KR101363153B1 (ko) 2014-02-13
ES2355523T5 (es) 2015-09-21
WO2007025944A1 (fr) 2007-03-08
JP2009506183A (ja) 2009-02-12
US8440601B2 (en) 2013-05-14
BRPI0614939A2 (pt) 2013-01-01
DE502006008293D1 (de) 2010-12-23

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