[go: up one dir, main page]

EP2201090B1 - 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 Download PDF

Info

Publication number
EP2201090B1
EP2201090B1 EP08839722A EP08839722A EP2201090B1 EP 2201090 B1 EP2201090 B1 EP 2201090B1 EP 08839722 A EP08839722 A EP 08839722A EP 08839722 A EP08839722 A EP 08839722A EP 2201090 B1 EP2201090 B1 EP 2201090B1
Authority
EP
European Patent Office
Prior art keywords
weight
mol
acid
carbon atoms
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP08839722A
Other languages
German (de)
English (en)
Other versions
EP2201090A2 (fr
Inventor
Heike Weber
Roland Ettl
Juergen Tropsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP08839722A priority Critical patent/EP2201090B1/fr
Priority to PL08839722T priority patent/PL2201090T3/pl
Publication of EP2201090A2 publication Critical patent/EP2201090A2/fr
Application granted granted Critical
Publication of EP2201090B1 publication Critical patent/EP2201090B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • 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
    • C11D3/40—Dyes ; Pigments
    • 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
    • C11D3/50—Perfumes

Definitions

  • 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 in a single detergent formulation are combined, so that for the consumer both the refilling of salt (in water 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 show, in particular, 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.
  • Other common polymers are polycarboxylates such as polyacrylic acids.
  • phosphate-based 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 (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.
  • 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 specific chelants as a builder system in dishwashing detergent formulations.
  • WO 02/34870 describes the combination of hydrophobically modified polycarboxylates, acrylic acid (co) polymers and phosphonates to give an antiscaling and 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 give 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.
  • 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-octadene, 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 20 -C 24 -alpha-olefins and Polyisobutene with an average of 12 to 100 carbon atoms.
  • Particularly preferred hydrophobically modified polycarboxylates contain both monomers a11), which are selected from maleic acid, maleic anhydride and acrylic acid, and also 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 20 C 24 -alpha-olefins and polyisobutene having 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) to 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) is in the hydrophilically modified polycarboxylates II to 0 to 50 mol .-%, preferably to 5 to 40 mol .-%, particularly preferably from 10 to 35 mol% and especially to 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 methacrylate being particularly preferred.
  • the polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.
  • the proportion of nonionic monomers 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 to say turbidity only above this calcium concentration 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, hydroxyiminodisuccinic acid, Ethylenediamine disuccinic acid, aspartic acid diacetic acid and salts thereof.
  • 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 .-%.
  • 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 are also suitable.
  • suitable nonionic surfactants are the EP-A 851 023 as well as the DE-A 198 19 187 ,
  • the formulations may further contain anionic 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.
  • the cleaning formulations according to the invention comprise 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 as well as 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-diperoxyazelain 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-diperoxyazelain acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-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 bleach 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 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 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
  • Bleach activators are preferably suitable from the group consisting of polyacylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, acylated phenolsulfonates, more preferably n- or iso-NOBS, MMA and TMAQ.
  • Bleach activators are used in amounts of generally 0.1 to 10 wt .-%, preferably from 1 to 9 wt .-%, particularly preferably from 1.5 to 8 wt .-%, 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 of the invention may contain 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, 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.
  • EP-A 446 982 and EP-A 453 003 known sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes may be present 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-analogues consisting of DE-A 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in DE-A 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which DE-A 196 20 411 known cobalt, iron, copper and ruthenium-amine complexes which are known in DE-A 44 16 438 described manganese, copper and cobalt complexes, which in EP-A 272 030 described cobalt complexes consisting of EP-A 693 550 known manganese complexes that are made EP-A 392 592 known manganese,
  • 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 ,
  • 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 metal silicates and mixtures of the aforementioned substances preference being given to using ammonium and / or alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate 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.
  • 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.
  • ballast dirt were added to the dishwasher at the beginning of the experiment. The test was carried out under the following rinsing conditions.
  • 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.

Landscapes

  • 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)

Claims (5)

  1. Formulations de nettoyage sans phosphate pour le lavage de la vaisselle en machine, contenant en tant que composants :
    a) 1 à 20 % en poids d'un mélange de polycarboxylates modifiés hydrophobiquement a1) et de polycarboxylates modifiés hydrophiliquement a2) de
    a1) 5 à 95 % en poids de polycarboxylates modifiés hydrophobiquement I de
    a11) 20 à 80 % en moles d'au moins un monomère du groupe constitué par les acides mono- ou dicarboxyliques en C3-C10 monoéthyléniquement insaturés ou leurs anhydrides,
    a12) 0 à 80 % en moles d'au moins un monomère de formule générale (I)
    Figure imgb0011
    dans laquelle R1, R2 et R3 signifient indépendamment les uns des autres H, CH3 ou C2H5,
    R4 signifie un radical linéaire, ramifié ou cyclique de 1 à 6 atomes de carbone ou un radical aromatique de 6 à 12 atomes de carbone,
    et
    a13) 0 à 20 % en moles d'au moins un monomère supplémentaire, choisi dans le groupe constitué par les oléfines de 10 atomes de carbone ou plus ou leurs mélanges et les polyisobutènes réactifs contenant en moyenne 12 à 100 atomes de carbone,
    a2) 5 à 95 % en poids de polycarboxylates modifiés hydrophiliquement II de
    a21) 50 à 99 % en moles d'acide acrylique et/ou d'un sel soluble dans l'eau de l'acide acrylique,
    a22) 0 à 50 % en moles d'un autre monomère acide et/ou d'un sel soluble dans l'eau de celui-ci,
    a23) 0,1 à 20 % en moles d'au moins un monomère non ionique de formule générale (II)
    Figure imgb0012
     dans laquelle les variables ont la signification suivante :
    R5 hydrogène ou méthyle,

            Z-C(O)O- ou -CH2O-

    R6 radicaux alkylène en C2-C4 non ramifiés ou ramifiés identiques ou différents,
    R7 alkyle en C1-C6 non ramifié ou ramifié,
    n 3 à 50,
    la somme de a1) et a2) étant de 100 % en poids,
    b) 0 à 50 % en poids d'un agent complexant,
    c) 0,1 à 20 % 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 supports d'alcalis, des inhibiteurs de corrosion, des agents antimousse, des colorants, des parfums, des charges, des solvants organiques et de l'eau,
    la somme des composants a) à g) étant de 100 % en poids.
  2. Formulation de nettoyage sans phosphate selon la revendication 1, caractérisée en ce que, dans le polycarboxylate modifié hydrophobiquement a1), les monomères a11) sont choisis dans le groupe constitué par l'acide maléique, l'anhydride de l'acide maléique et l'acide acrylique, les monomères a12) sont choisis dans le groupe constitué par l'isobutène, le diisobutène et le styrène et les monomères a13) dans le groupe constitué par le 1-dodécène, le 1-octadécène, une alpha-oléfine en C22, un mélange d'alpha-oléfines en C20 à C24 et le polyisobutène contenant en moyenne 12 à 100 atomes C.
  3. Formulation de nettoyage sans phosphate selon la revendication 1 ou 2, caractérisée en ce que les polycarboxylates modifiés hydrophiliquement présentent une résistance au calcium correspondant à un point de trouble d'une solution contenant 250 mg/L du polymère modifié hydrophiliquement à pH 10 à une concentration en calcium > 2 000 mg/L Ca2+.
  4. Formulation de nettoyage sans phosphate selon l'une quelconque des revendications 1 à 3, caractérisée en ce que l'agent complexant b) est choisi dans le groupe constitué par l'acide nitrilotriacétique, l'acide hydroxyéthyléthylène-diamine-triacétique, l'acide éthylène-diamine-tétraacétique, l'acide diéthylène-triamine-pentaacétique et l'acide méthylglycidine-diacétique, l'acide glutaminique-diacétique, l'acide iminodisuccinique, l'acide hydroxyiminodisuccinique, l'acide éthylènediamine-disuccinique, l'acide asparaginique-diacétique et leurs sels.
  5. Utilisation d'un mélange de polycarboxylates modifiés hydrophobiquement et de polycarboxylates modifiés hydrophiliquement de
    a1) 5 à 95 % en poids de polycarboxylates modifiés hydrophobiquement (I) de
    a11) 20 à 80 % en moles d'au moins un monomère du groupe constitué par les acides mono- ou dicarboxyliques en C3-C10 monoéthyléniquement insaturés ou leurs anhydrides,
    a12) 0 à 80 % en moles d'au moins un monomère de formule générale (I)
    Figure imgb0013
    dans laquelle R1, R2 et R3 signifient indépendamment les uns des autres H, CH3 ou C2H5,
    R4 signifie un radical linéaire, ramifié ou cyclique de 1 à 6 atomes de carbone ou un radical aromatique de 6 à 12 atomes de carbone,
    et
    a13) 0 à 20 % en moles d'au moins un monomère supplémentaire, choisi dans le groupe constitué par les oléfines de 10 atomes de carbone ou plus ou leurs mélanges et les polyisobutènes réactifs contenant en moyenne 12 à 100 atomes de carbone,
    a2) 5 à 95 % en poids de polycarboxylates modifiés hydrophiliquement II de
    a21) 50 à 99 % en moles d'acide acrylique et/ou d'un sel soluble dans l'eau de l'acide acrylique,
    a22) 0 à 50 % en moles d'un autre monomère acide et/ou d'un sel soluble dans l'eau de celui-ci,
    a23) 0,1 à 20 % en moles d'au moins un monomère non ionique de formule générale (II)
    Figure imgb0014
     dans laquelle les variables ont la signification suivante :
    R5 hydrogène ou méthyle,

            Z-C(O)O- ou -CH2O-

    R6 radicaux alkylène en C2-C4 non ramifiés ou ramifiés identiques ou différents,
    R7 alkyle en C1-C6 non ramifié ou ramifié,
    n 3 à 50,
    la somme de a1) et a2) étant de 100 % en poids,
    en tant que co-adjuvant dans des formulations de nettoyage pour le lavage de la vaisselle en machine.
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
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
PL08839722T PL2201090T3 (pl) 2007-10-12 2008-10-10 Preparaty czyszczące do mycia naczyń zawierające mieszaninę hydrofobowo zmodyfikowanych polikarboksylanów i hydrofilowo zmodyfikowanych polikarboksylanów

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07118356 2007-10-12
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
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

Publications (2)

Publication Number Publication Date
EP2201090A2 EP2201090A2 (fr) 2010-06-30
EP2201090B1 true EP2201090B1 (fr) 2011-08-31

Family

ID=40276047

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08839722A Not-in-force 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

Country Status (13)

Country Link
US (1) US8262804B2 (fr)
EP (1) EP2201090B1 (fr)
JP (1) JP5606319B2 (fr)
KR (1) KR101529351B1 (fr)
CN (1) CN101821370B (fr)
AT (1) ATE522595T1 (fr)
AU (1) AU2008313803B2 (fr)
BR (1) BRPI0818439B1 (fr)
CA (1) CA2702425C (fr)
ES (1) ES2371698T3 (fr)
MX (1) MX2010003792A (fr)
PL (1) PL2201090T3 (fr)
WO (1) WO2009050123A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9683203B2 (en) 2013-11-11 2017-06-20 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
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

Families Citing this family (23)

* 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
CN110105480A (zh) 2013-03-15 2019-08-09 路博润先进材料公司 衣康酸聚合物
CN105102602B (zh) * 2013-04-02 2018-05-25 巴斯夫欧洲公司 配制剂、其作为或用于制品器皿洗涤清净剂的用途及其制备
WO2015042013A1 (fr) 2013-09-18 2015-03-26 Lubrizol Advanced Materials, Inc. Polymères linéaires stables
EA201691672A1 (ru) * 2014-02-20 2017-02-28 Юнилевер Н.В. Композиция для посудомоечной машины
JP7071039B2 (ja) 2014-03-14 2022-05-18 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド イタコン酸ポリマーおよびコポリマー
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
BR112017018859B1 (pt) 2015-03-20 2022-12-13 Rohm And Haas Company Composição de detergente para lavagem automática de louças e método de limpeza de um artigo em uma máquina de lavar louças automática
FR3067718B1 (fr) * 2017-06-16 2020-08-14 Coatex Sas Composition detergente polymerique sans phosphate
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
US11421190B2 (en) * 2017-07-31 2022-08-23 Dow Global Technologies Llc Detergent additive
EP3788125B1 (fr) * 2018-05-02 2024-03-13 Basf Se Compositions détergentes pour le lavage de la vaisselle comprenant de l'acide polyaspartique et des polymères greffés à base d'oligo et de polysaccharides comme additifs inhibiteurs de film
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
CN113795569B (zh) * 2019-06-05 2023-10-13 陶氏环球技术有限责任公司 自动餐具洗涤组合物和清洁物品的方法
EP3990601A1 (fr) 2019-08-06 2022-05-04 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
US20230106979A1 (en) * 2020-02-28 2023-04-06 Conopco Inc., D/B/A Unilever Dishwash detergent product

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
DE69125309T2 (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
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
CA2083661A1 (fr) 1991-11-26 1993-05-27 Rudolf J. Martens Compositions pour detersif
CA2085642A1 (fr) 1991-12-20 1993-06-21 Ronald Hage Activation de blanchiment
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
GB9305863D0 (en) 1993-03-22 1993-05-12 Unilever Plc Peroxyacids
ATE182617T1 (de) 1993-05-20 1999-08-15 Procter & Gamble Bleichmittelzusammensetzungen enthaltend n- acylcaprolactam aktivatoren
CA2161213A1 (fr) 1993-05-20 1994-12-08 Alan David Willey Composes de blanchiment renfermant du caprolactame n-acyle pour lavage a la main ou autres methodes de nettoyage utilisant peu d'eau
CN1066715C (zh) 1993-05-20 2001-06-06 普罗格特-甘布尔公司 包含取代的苯甲酰基己内酰胺漂白活化剂的漂白化合物
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
EP0693550B1 (fr) 1994-07-21 2004-06-16 Ciba SC Holding AG Composition de blanchiment de tissu
DE4443177A1 (de) 1994-12-05 1996-06-13 Henkel Kgaa Aktivatormischungen für anorganische Perverbindungen
WO1996027000A1 (fr) * 1995-02-28 1996-09-06 Kay Chemical Company Gel liquide concentre constituant un detergent de lavage de vaisselle
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
DE19616770A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acyllactame als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616769A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acylacetale als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616693A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616767A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa 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
WO2002034870A1 (fr) * 2000-10-25 2002-05-02 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

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9683203B2 (en) 2013-11-11 2017-06-20 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
US10745651B2 (en) 2013-11-11 2020-08-18 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US11339354B2 (en) 2013-11-11 2022-05-24 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US11920109B2 (en) 2013-11-11 2024-03-05 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US12371640B2 (en) 2013-11-11 2025-07-29 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
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

Also Published As

Publication number Publication date
CN101821370B (zh) 2013-01-30
AU2008313803B2 (en) 2014-01-30
CA2702425A1 (fr) 2009-04-23
ES2371698T3 (es) 2012-01-09
JP2011500878A (ja) 2011-01-06
BRPI0818439B1 (pt) 2017-07-04
US20100234265A1 (en) 2010-09-16
EP2201090A2 (fr) 2010-06-30
PL2201090T3 (pl) 2012-01-31
CA2702425C (fr) 2016-02-23
KR101529351B1 (ko) 2015-06-17
CN101821370A (zh) 2010-09-01
ATE522595T1 (de) 2011-09-15
US8262804B2 (en) 2012-09-11
JP5606319B2 (ja) 2014-10-15
WO2009050123A3 (fr) 2009-06-18
MX2010003792A (es) 2010-07-06
KR20100097105A (ko) 2010-09-02
BRPI0818439A2 (pt) 2015-05-12
AU2008313803A1 (en) 2009-04-23
WO2009050123A2 (fr) 2009-04-23

Similar Documents

Publication Publication Date Title
EP2201090B1 (fr) Formulations de détergents pour la vaisselle, contenant un mélange de polycarboxylates à modification hydrophobe et de polycarboxylates à modification hydrophile
EP1791936B1 (fr) Formulations de nettoyage pour un nettoyage de la vaisselle en machine contenant du polycarboxylate modifie de maniere hydrophobe
EP1924676B1 (fr) Preparations detergentes pour lavage en lave-vaisselle contenant des polycarboxylates a modification hydrophile
EP1924675B2 (fr) Preparations detergentes pour lavage en lave-vaisselle contenant des polycarboxylates a modification hydrophile
EP2052066A1 (fr) Formulation de nettoyage pour des lave-vaisselle
EP2113024B1 (fr) Détergent pour la vaisselle
EP3068859B1 (fr) Composition detergente pour lave vaiselle et son utilisation
WO2012098177A1 (fr) Utilisation d'alcooléthoxylates de suif en lavage en lave-vaisselle
DE102008000029A1 (de) Geschirrreinigungsmittel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100512

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502008004715

Country of ref document: DE

Effective date: 20111027

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2371698

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20120109

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20110831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111231

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111130

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111201

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120102

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111031

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20120601

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502008004715

Country of ref document: DE

Effective date: 20120601

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20121025

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20121129

Year of fee payment: 5

Ref country code: SE

Payment date: 20121026

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20121024

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111010

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110831

BERE Be: lapsed

Owner name: BASF SE

Effective date: 20131031

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20140501

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131011

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 522595

Country of ref document: AT

Kind code of ref document: T

Effective date: 20131010

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131010

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20161031

Year of fee payment: 9

Ref country code: GB

Payment date: 20161028

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20161125

Year of fee payment: 9

Ref country code: IT

Payment date: 20161021

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20170102

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20170920

Year of fee payment: 10

Ref country code: PL

Payment date: 20170920

Year of fee payment: 10

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502008004715

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20171010

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20180629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171010

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171010

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20181220

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181010

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181010