EP2201090A2 - Formulations de détergents pour la vaisselle, contenant un mélange de polycarboxylates à modification hydrophobe et de polycarboxylates à modification hydrophile - Google Patents

Formulations de détergents pour la vaisselle, contenant un mélange de polycarboxylates à modification hydrophobe et de polycarboxylates à modification hydrophile

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Publication number
EP2201090A2
EP2201090A2 EP08839722A EP08839722A EP2201090A2 EP 2201090 A2 EP2201090 A2 EP 2201090A2 EP 08839722 A EP08839722 A EP 08839722A EP 08839722 A EP08839722 A EP 08839722A EP 2201090 A2 EP2201090 A2 EP 2201090A2
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acid
mol
monomer
carbon atoms
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EP08839722A
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German (de)
English (en)
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EP2201090B1 (fr
Inventor
Heike Weber
Roland Ettl
Juergen Tropsch
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BASF SE
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BASF SE
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Priority to PL08839722T priority Critical patent/PL2201090T3/pl
Priority to EP08839722A priority patent/EP2201090B1/fr
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes

Definitions

  • Dishwashing formulations comprising a mixture of hydrophobically modified polycarboxylates and hydrophilically modified polycarboxylates
  • the invention relates to cleaning formulations for machine dishwashing.
  • the items to be washed should be produced in a residue-free, cleaned condition with an impeccably glossy surface.
  • the items to be washed must be cleaned of food residues and the detached contaminants must be dispersed or emulsified so that they do not re-deposit on the dishes surfaces.
  • no whitish spots or deposits should occur, which arise due to the presence of lime or other inorganic and organic salts in the drying of water droplets or reflected by deposition of dirt or inorganic salts already during the rinsing process.
  • the multifunctional cleaners eg 3-in-1 cleaners
  • the functions of cleaning, rinsing and water softening are combined in a single detergent formulation, so that for the consumer both the refilling of salt (in water hardness from 0 ° to 21 °) as well as rinse aid becomes superfluous.
  • polymers are frequently used for inhibiting coating. These may be, for example, sulfonate-containing polymers in phosphate-containing cleaners, which in particular show effects on the inhibition of calcium phosphate precipitates.
  • the surfactants used are chosen so that they drag themselves into the rinse cycle, where they ensure optimal wetting and a good rinse aid result.
  • Further customary polymers are polycarboxylates, such as polyacrylic acids.
  • phosphate-based B07 / 0663PC IB / XS / arw / cd
  • Many of the formulations on the market are phosphate-based.
  • the phosphate used is ideal for use because it combines many useful properties that are needed in machine dishwashing.
  • phosphate is able to disperse water hardness (ie 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.
  • EP-A 0 778 340 describes the use of copolymers of allyl alcohol ethoxylates and acrylic acid in phosphate-free dishwashing detergent compositions.
  • WO2005 / 042684 describes the use of special copolymers of acrylic acid, methacrylic acid and acrylic acid alkoxylates as deposit-inhibiting additives in machine dishwashing.
  • WO2006 / 029806 describes the use of a combination of specific hydrophobically modified polycarboxylates and special complexing agents as a builder system in dishwashing detergent formulations.
  • WO 02/34870 describes the combination of hydrophobically modified polycarboxylates, acrylic acid (co) polymers and phosphonates for the production of an antiscaling and an antispotting effect. Both phosphate-containing and phosphate-free dishwashing detergents are described.
  • the object of the invention is to provide improved phosphate-free cleaning formulations for machine dishwashing which result in an improved dishwashing result.
  • 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.
  • phosphate-free cleaning formulations for machine dishwashing containing as components:
  • R 1 , R 2 and R 3 independently of one another, denote H, CH 3 or C 2 H 5 ,
  • R 4 represents a linear, branched or cyclic radical having 1 to 6 carbon atoms or an aromatic radical having 6 to 12 carbon atoms
  • R 5 is hydrogen or methyl
  • R 6 identical or different unbranched or branched C 2 -C 4 - alkylene radicals
  • R 7 is unbranched or branched C 1 -C 6 -alkyl
  • g from 0 to 50% by weight of one or more further additives, such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors,
  • B07 / 0663PC doors defoamers, dyes, fragrances, fillers, tablet explosives, organic solvents and water,
  • the formulation may be processed as a tablet, powder, gel, capsule or solution. These may be formulations for both household and commercial applications.
  • the object is further achieved by the use of a combination of hydrophobically modified polycarboxylates a1) and hydrophilic modified polycarboxylates a2) as co-builders in cleaning formulations for machine dishwashing.
  • Suitable monomers a11) for the hydrophobically modified polycarboxylates a1) are, for example, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid.
  • Preferred hydrophobically modified polycarboxylates a1) contain as monomers a11) monomers which are selected from the group consisting of maleic acid, maleic anhydride and acrylic acid.
  • Suitable monomers a12) are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene.
  • Further preferred hydrophobically modified polycarboxylates a1) contain as monomers a12) monomers which are selected from the group consisting of isobutene, diisobutene and styrene.
  • Suitable monomers a13) have at least 10, generally 10-26, carbon atoms.
  • Suitable monomers a13) are, for example, 1-decene, 1-dodecane, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docoses, 1-tetracoses and 1-hexacoses.
  • hydrophobically modified polycarboxylates a1) contain as monomers a13) monomers which are selected from the group consisting of 1-dodecene, 1-octadecene, C 22 -alpha-olefin, a mixture of C 2 oC 24 -alpha-olefins and polyisobutene having an average of 12 to 100 carbon atoms.
  • hydrophobically modified polycarboxylates contain both monomers a1 1), which are selected from maleic acid, maleic anhydride and acrylic
  • B07 / 0663PC acid as well as monomers a12), which are selected from isobutene, diisobutene and styrene, as well as monomers a13), which are selected from the group consisting of 1-dodecene, 1-octadecene, C 22 -alpha-olefin, a mixture of C 2 oC 24 -alpha-olefins and polyisobutene with an average of 12 to 100 carbon atoms.
  • the hydrophilically modified polycarboxylates II contain as copolymerized components a21) and a22) acrylic acid, optionally a further acidic monomer, 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 a21) on the hydrophilically modified polycarboxylates II is 50 to 99 mol%, preferably 55 to 90 mol% and particularly preferably 60 to 85 mol%.
  • the further acidic monomer a22) in the hydrophilically modified polycarboxylates II is 0 to 50 mol%, preferably 5 to 40 mol%, particularly preferably 10 to 35 mol% and especially 15 to 30 mol. -% contain.
  • Acid monomers a22) are, for example, methacrylic acid, maleic acid, sulfonate groups or phosphonate group-containing monomers, preference being given to methacrylic acid and maleic acid.
  • nonionic monomers (a23) are: allyl alcohol, 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 - Kolmethacrylat 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 a23) to the hydrophilically modified polycarboxylates II is 0.1 to 20 mol .-%, preferably 1 to 15 mol .-% and especially 2 to 10 mol .-%.
  • the ethoxylated allyl alcohol a23) is preferably alkoxylated with 5 to 40 mol, more preferably with 10 to 30 mol of ethylene oxide.
  • the weight-average molecular weight M w of the hydrophilically modified polycarboxylates a2) is generally 500 to 500,000 g / mol, preferably 1000 to 300,000 g / mol, particularly preferably 5,000 to 100,000 g / mol.
  • the hydrophilically modified polycarboxylates preferably have a calcium insensitivity, which corresponds to a cloud point of a solution containing 250 mg / L of the hydrophilically modified polymer at pH 10 at a calcium concentration of> 2000 mg / L Ca 2+ , that is, only above this calcium concentration occurs a clouding of the polymer solution by precipitation of calcium salts.
  • the cleaning formulations according to the invention contain 1 to 20 wt .-%, preferably 1 to 10 wt .-% of the mixture of hydrophobically modified polycarboxylates a1) and hydrophilic modified polycarboxylates a2), wherein the proportion of hydrophobically modified polycarboxylates a1) 5 to 95 wt. %, preferably 10 to 90 wt .-% and particularly preferably 20 to 80 wt .-%, and the proportion of hydrophilically modified polycarboxylates a2) 5 to 95 wt .-%, preferably 10 to 90 wt .-% and particularly preferably 20 to 80 wt .-%, based on the sum of a1) and a2), is.
  • the cleaning formulations according to the invention may contain one or more complexing agents.
  • Preferred complexing agents are selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid and methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyl
  • Particularly preferred complexing agents b) are methylglycinediacetic acid and its salts.
  • the cleaning formulations according to the invention contain weakly or low-foaming nonionic surfactants. These are generally present in proportions of 0.1 to 20 wt .-%, preferably 0.1 to 15 wt .-%, particularly preferably 0.25 to 10 wt .-%.
  • Suitable nonionic surfactants include the surfactants of general formula (III)
  • R 2 is a linear or branched alkyl radical having 8 to 22 carbon atoms
  • R 1 and R 3 are independently hydrogen or a linear or branched alkyl radical having 1-10 C atoms or H, wherein R 1 is preferably methyl
  • p and m are independently 0 to 300.
  • the surfactants of formula (III) may be both random copolymers and block copolymers, preferably block copolymers.
  • 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 is given by EP-A 851 023 and DE-A 198 19 187.
  • the formulations may further contain anionic or zwitterionic surfactants, preferably in admixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are also mentioned in EP-A 851 023 and DE-A 198 19 187.
  • Bleaching agents and optionally bleach activators are optionally bleach activators.
  • Bleaching agents are subdivided into oxygen bleaching agents and chlorine-containing bleaching agents. Use as oxygen bleaching agents find alkali metal perborates and their hydrates
  • bleaching agents 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-diperoxazelainic acid, diperoxoisophthalic acid or 2-decyldiperoxybutan-1, 4- dioic.
  • organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxazelainic acid, diperoxoisophthalic acid or 2-decyldiperoxybutan-1, 4- dioic.
  • 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 bleach with peroxide-containing bleaches may 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 sulfondichloroamid 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, under perhydrolysis conditions, comprise aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to
  • B07 / 0663PC 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, for example, N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, for example n-nonanoyl- or isononanoyloxybenzenesulfonates (n- or iso-NOBS), pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (DADHT) or isatoic anhydride (ISA).
  • nitrile quats such as N-methyl morpholinium acetonitrile salts (MMA salts) or trimethyl ammonium
  • Bleach activators are preferably suitable from the group consisting of multiply acylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, 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 acetylated sorbitol and mannitol and 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 94/27 970, WO
  • hydrophilic substituted acylacetals listed in DE-A 196 16 769 and the acyl lactams described in DE-A 196 16 770 and WO 95/14075 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; oxidized starches, oxidized polysaccharides; homo- and copolymeric polycarboxylic acids and their salts, such as polyacrylic acid, polymethacrylic acid, copolymers of maleic acid and acrylic acid;
  • the cleaning formulations of the invention may contain enzymes. Between 0 and 8% by weight of enzymes, based on the total preparation, can be added to the cleaning agent in order to increase the performance of the cleaning agents or to ensure the cleaning performance in the same quality under milder conditions.
  • 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, disintegrating agents, organic solvents and water.
  • further additives such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, disintegrating agents, organic solvents and water.
  • B07 / 0663PC and / or bleach-enhancing transition metal salts or transition metal complexes may 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-salene complexes known from DE-A 195 29 905 and their N-analogues known from DE-A 196 20 267, which consist of DE-A 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl, the described in DE-A 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium-amine complexes known from DE-A 196 20 41 1, the manganese, copper and cobalt described in DE-A 44 16 438 Complexes, the cobalt complexes described in EP-A 272 030, the manganese complexes known from EP-A 693 550, the manganese, iron, cobalt and copper
  • TMTACN 1, 4,7-trimethyl-1, 4,7-triazacyclononane
  • PF6 ⁇ PF6 ⁇
  • 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 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 ,
  • 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.
  • B07 / 0663PC Ammonium and / or alkali metal silicates and mixtures of the abovementioned substances, preference being given to using ammonium and / or alkali metal carbonates, in particular sodium carbonate, sodium hydrogencarbonate or sodium sesquicarbonate.
  • 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 manganese sulfate used.
  • zinc compounds or bismuth compounds can be used to prevent corrosion on the items to be washed.
  • 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.
  • Polymer 1 copolymer of maleic acid and diisobutene (weight ratio 51:49) having a molecular weight of 12,000 g / mol;
  • Polymer 2 copolymer of maleic anhydride, isobutene and C18 olefin (weight ratio 65: 26: 9), molecular weight 3,000 g / mol;
  • Polymer 3 polyacrylic acid, molecular weight 4000 g / mol;
  • Polymer 4 copolymer of acrylic acid, maleic acid and allyl alcohol, ethoxylated with 16.6 moles of ethylene oxide per mole of allyl alcohol, in the molar ratio 82.5: 15: 2.5, with a K value of 74.5 at pH 7 in 1 wt. -% solution at 25 0 C;
  • ballast dirt were added to the dishwasher at the beginning of the experiment. The test was carried out under the following rinsing conditions.
  • Dishwasher Miele G 686 SC Rinses: 2 rinses 55 ° C Normal (without pre-rinsing) Wash ware: knife (WMF table knife Berlin, monoblock) and keg glass cup (Matador, Ruhr Kristall),
  • the evaluation of the dishes was carried out 18 hours after cleaning by visual inspection in a black painted light box with halogen spot and pinhole.
  • the coverings on knives and glasses were rated on a grading scale from 10 (very good) to 1 (very bad).
  • the highest grade of 10 corresponds to a surface free of deposits, from grades ⁇ 5 coverings are already recognizable with normal room lighting, so 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP08839722A 2007-10-12 2008-10-10 Formulations de détergents pour la vaisselle, contenant un mélange de polycarboxylates à modification hydrophobe et de polycarboxylates à modification hydrophile Not-in-force EP2201090B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL08839722T PL2201090T3 (pl) 2007-10-12 2008-10-10 Preparaty czyszczące do mycia naczyń zawierające mieszaninę hydrofobowo zmodyfikowanych polikarboksylanów i hydrofilowo zmodyfikowanych polikarboksylanów
EP08839722A EP2201090B1 (fr) 2007-10-12 2008-10-10 Formulations de détergents pour la vaisselle, contenant un mélange de polycarboxylates à modification hydrophobe et de polycarboxylates à modification hydrophile

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07118356 2007-10-12
PCT/EP2008/063646 WO2009050123A2 (fr) 2007-10-12 2008-10-10 Formulations de détergents pour la vaisselle, contenant un mélange de polycarboxylates à modification hydrophobe et de polycarboxylates à modification hydrophile
EP08839722A EP2201090B1 (fr) 2007-10-12 2008-10-10 Formulations de détergents pour la vaisselle, contenant un mélange de polycarboxylates à modification hydrophobe et de polycarboxylates à modification hydrophile

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CN (1) CN101821370B (fr)
AT (1) ATE522595T1 (fr)
AU (1) AU2008313803B2 (fr)
BR (1) BRPI0818439B1 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015070117A1 (fr) 2013-11-11 2015-05-14 Ecolab Usa Inc. Détergent de lavage fortement alcalin offrant un meilleur contrôle du tartre et une meilleure dispersion des salissures

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009017724A1 (de) * 2009-04-11 2010-10-14 Clariant International Limited Bleichmittelgranulate
JP5491770B2 (ja) * 2009-05-29 2014-05-14 花王株式会社 自動食器洗浄機用洗浄剤組成物
JP5491773B2 (ja) * 2009-06-10 2014-05-14 花王株式会社 自動食器洗浄機用洗浄剤組成物
SG173230A1 (en) * 2010-01-25 2011-08-29 Rohm & Haas Laundry detergent bar composition
JP5834261B2 (ja) * 2010-09-30 2015-12-16 サンノプコ株式会社 加水分解用助剤及びこれを用いた糖質の加水分解方法
DE102011119332A1 (de) * 2011-11-25 2013-05-29 Centrum Für Angewandte Nanotechnologie (Can) Gmbh Verwendung von über radikalische Emulsionspolymerisation erhältlichen Polymeren als Verdicker für Reinigungsmittel
WO2014143773A1 (fr) 2013-03-15 2014-09-18 Lubrizol Advanced Materials, Inc. Polymères d'acide itaconique
WO2014161786A1 (fr) * 2013-04-02 2014-10-09 Basf Se Formulations, leur utilisation comme produits de lavage de la vaisselle ou pour la production de tels produits, et leur préparation
WO2015042013A1 (fr) 2013-09-18 2015-03-26 Lubrizol Advanced Materials, Inc. Polymères linéaires stables
PT3107987T (pt) 2014-02-20 2019-01-17 Unilever Nv Composição de lavagem de louça à máquina
BR112016021154A2 (pt) 2014-03-14 2021-08-24 Lubrizol Advanced Materials, Inc. Polímeros e copolímeros de ácido itacônico
CN104001627B (zh) * 2014-05-12 2016-09-14 昆明理工大学 一种选择性抑制白钨矿矿石中含钙脉石矿物的抑制剂
PL3271446T3 (pl) 2015-03-20 2022-11-07 Rohm And Haas Company Detergent do automatycznego zmywania naczyń
FR3067718B1 (fr) * 2017-06-16 2020-08-14 Coatex Sas Composition detergente polymerique sans phosphate
US11421190B2 (en) * 2017-07-31 2022-08-23 Dow Global Technologies Llc Detergent additive
JP7231611B2 (ja) * 2017-07-31 2023-03-01 ダウ グローバル テクノロジーズ エルエルシー 洗剤添加剤
CN109665634A (zh) * 2019-01-30 2019-04-23 上海电力学院 一种高分子阻垢缓蚀剂及其制备方法和应用
WO2021026292A1 (fr) 2019-08-06 2021-02-11 Ecolab Usa Inc. Composition détergente contenant un tétrapolymère d'acide maléique
DE102019126683A1 (de) * 2019-10-02 2021-04-08 Henkel Ag & Co. Kgaa Copolymere zur Verbesserung der Lagerstabilität von Enzymen in Wasch- und Reinigungsmitteln
KR102266427B1 (ko) * 2019-11-27 2021-06-18 애경산업(주) 의류용 액체 세제 조성물
CN115210349A (zh) * 2020-02-28 2022-10-18 联合利华知识产权控股有限公司 餐具洗涤剂产品
WO2024089079A1 (fr) 2022-10-25 2024-05-02 Symrise Ag Composition de nettoyage de vaisselle et/ou de rinçage de vaisselle présentant des propriétés de finition améliorées

Family Cites Families (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8629837D0 (en) 1986-12-13 1987-01-21 Interox Chemicals Ltd Bleach activation
US5245075A (en) 1987-11-13 1993-09-14 Ausimont S.R.L. Peroxy carboxylic amino derivatives
US5292447A (en) 1988-06-14 1994-03-08 Ausimont S.R.L. Heterocyclic peroxides having n-amidic heteroatoms
US5039447A (en) 1988-12-12 1991-08-13 Monsanto Company Pourable sulfone peracid compositions
GB8908416D0 (en) 1989-04-13 1989-06-01 Unilever Plc Bleach activation
GB9003741D0 (en) 1990-02-19 1990-04-18 Unilever Plc Bleach activation
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
US5041232A (en) 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
DE69125310T2 (de) 1990-05-21 1997-07-03 Unilever Nv Bleichmittelaktivierung
ATE155165T1 (de) 1991-07-31 1997-07-15 Ausimont Spa Verfahren zur erhöhung der bleichwirksamkeit eines inorganischen persalzes
EP0544490A1 (fr) 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
CA2085642A1 (fr) 1991-12-20 1993-06-21 Ronald Hage Activation de blanchiment
GB9305863D0 (en) 1993-03-22 1993-05-12 Unilever Plc Peroxyacids
CA2161214C (fr) 1993-05-20 2000-06-27 Alan David Willey Composes de blanchiment renfermant des activateurs de blanchiment a base de derive de substitution benzoylique de caprolactame
AU6833394A (en) 1993-05-20 1994-12-20 Procter & Gamble Company, The Bleaching compounds comprising n-acyl caprolactam for use in hand-wash or other low-water cleaning systems
DE69419750T2 (de) 1993-05-20 2000-05-31 Procter & Gamble Bleichmittelzusammensetzungen enthaltend n-acylcaprolactam aktivatoren
US5405413A (en) 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
DE4338922A1 (de) 1993-11-15 1995-05-18 Degussa Aktivatoren für anorganische Persauerstoffverbindungen
WO1995014759A1 (fr) 1993-11-25 1995-06-01 Warwick International Group Limited Compositions de blanchiment
US5534196A (en) 1993-12-23 1996-07-09 The Procter & Gamble Co. Process for making lactam bleach activator containing particles
MX9604643A (es) 1994-04-07 1997-11-29 Procter & Gamble Composiciones blanqueadoras que consisten de catalizadores de blanqueo que contienen metal.
DE4416438A1 (de) 1994-05-10 1995-11-16 Basf Ag Ein- oder mehrkernige Metall-Komplexe und ihre Verwendung als Bleich- und Oxidationskatalysatoren
DE69533149T2 (de) 1994-07-21 2005-08-25 Ciba Specialty Chemicals Holding Inc. Bleichmittelzusammensetzung für Gewebe
DE4443177A1 (de) 1994-12-05 1996-06-13 Henkel Kgaa Aktivatormischungen für anorganische Perverbindungen
CN1105181C (zh) * 1995-02-28 2003-04-09 凯化学公司 浓缩液体凝胶器皿洗涤剂
DE19529905A1 (de) 1995-08-15 1997-02-20 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
DE19536082A1 (de) 1995-09-28 1997-04-03 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
EP0778340A3 (fr) 1995-12-06 1999-10-27 Basf Corporation Compositions exemptes de phosphate pour le lavage en lave-vaisselle contenant des copolymères à base de produits d'addition d'oxyde d'alkylène d'alcool allylique et d'acide acrylique
DE19605688A1 (de) 1996-02-16 1997-08-21 Henkel Kgaa Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19613103A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallkomplex-haltige Systeme als Aktivatoren für Persauerstoffverbindungen
DE19620411A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallamminkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19616769A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acylacetale als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616767A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616693A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616770A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acyllactame als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19620267A1 (de) 1996-05-20 1997-11-27 Henkel Kgaa Katalytisch wirksame Aktivatorkomplexe mit N¶4¶-Liganden für Persauerstoffverbindungen
US5837663A (en) 1996-12-23 1998-11-17 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets containing a peracid
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
EP1328613B1 (fr) 2000-10-25 2006-09-20 Unilever Plc Compositions pour laver la vaisselle
DE10350420A1 (de) 2003-10-28 2005-06-02 Basf Ag Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren als belagsinhibierende Additive im Klarspülgang des maschinellen Geschirrspülers
DE102004044411A1 (de) * 2004-09-14 2006-03-30 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophob modifizierte Polycarboxylate
DE102005041349A1 (de) 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
DE102005041347A1 (de) * 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009050123A2 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015070117A1 (fr) 2013-11-11 2015-05-14 Ecolab Usa Inc. Détergent de lavage fortement alcalin offrant un meilleur contrôle du tartre et une meilleure dispersion des salissures
US9353335B2 (en) 2013-11-11 2016-05-31 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US10316272B2 (en) 2013-11-11 2019-06-11 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion

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CA2702425A1 (fr) 2009-04-23
CA2702425C (fr) 2016-02-23
KR20100097105A (ko) 2010-09-02
CN101821370A (zh) 2010-09-01
CN101821370B (zh) 2013-01-30
BRPI0818439B1 (pt) 2017-07-04
MX2010003792A (es) 2010-07-06
JP2011500878A (ja) 2011-01-06
PL2201090T3 (pl) 2012-01-31
US8262804B2 (en) 2012-09-11
KR101529351B1 (ko) 2015-06-17
EP2201090B1 (fr) 2011-08-31
WO2009050123A2 (fr) 2009-04-23
JP5606319B2 (ja) 2014-10-15
US20100234265A1 (en) 2010-09-16
BRPI0818439A2 (pt) 2015-05-12
AU2008313803A1 (en) 2009-04-23
WO2009050123A3 (fr) 2009-06-18
ES2371698T3 (es) 2012-01-09
AU2008313803B2 (en) 2014-01-30
ATE522595T1 (de) 2011-09-15

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