EP0944707B2 - Acetonitril-derivate als bleichaktivatoren in reinigungsmitteln - Google Patents

Acetonitril-derivate als bleichaktivatoren in reinigungsmitteln Download PDF

Info

Publication number
EP0944707B2
EP0944707B2 EP97951944A EP97951944A EP0944707B2 EP 0944707 B2 EP0944707 B2 EP 0944707B2 EP 97951944 A EP97951944 A EP 97951944A EP 97951944 A EP97951944 A EP 97951944A EP 0944707 B2 EP0944707 B2 EP 0944707B2
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
formula
compound corresponding
alkyl
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.)
Expired - Lifetime
Application number
EP97951944A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0944707B1 (de
EP0944707A2 (de
Inventor
Christian Nitsch
Rainer Jeschke
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7813058&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0944707(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP01115441A priority Critical patent/EP1138754A1/de
Publication of EP0944707A2 publication Critical patent/EP0944707A2/de
Publication of EP0944707B1 publication Critical patent/EP0944707B1/de
Application granted granted Critical
Publication of EP0944707B2 publication Critical patent/EP0944707B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
    • 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
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • 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

Definitions

  • the present invention relates to dishwashing detergents the certain acetonitrile derivatives as activators for in particular inorganic peroxygen compounds for bleaching colored stains Dishes included.
  • Inorganic peroxygen compounds especially hydrogen peroxide and solid peroxygen compounds. which dissolve in water releasing hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate. have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N- acylated hydantoins, hydrazides.
  • bleach activators for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N- acylated hydantoins, hydrazides.
  • Triazoles, hydrotriazines, urazoles, diketopiperazines, sulfuryl amides and cyanurates in addition to carboxylic acid anhydrides, especially phthalic anhydride, carboxylic esters, especially sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetyl-glucose. have become known in the literature. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased so much that even at temperatures around 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur.
  • Japanese Patent Application JP 1-198 700 discloses dishwashing compositions which contain ammonium acetonitrile derivatives whose quaternary nitrogen atom carries two C 1-3 alkyl groups and one C 1-22 alkyl group.
  • European patent application EP 0 464 880 discloses the use of similar substances having two C 1-4 alkyl or hydroxyalkyl groups and a C 1-24 alkyl, alkelnyl or alkyl ether group.
  • European Patent Application EP 0 303 520 discloses bleaching textile detergents containing ammonium acetonitrile derivatives whose quaternary nitrogen atom is part of an optionally substituted pyridine ring.
  • EP-A 0 790 244 relates to ammonium nitriles and their use as bleach activators.
  • the ammonium nitriles used have the general structure shown there on page 2, lines 40 to 50, wherein R 1 and R 2 together with the nitrogen atom to which they are attached form a ring having 4 to 6 carbon atoms, this ring in addition to Nitrogen atom may contain 1 or 2 oxygen or nitrogen atoms instead of carbon atoms.
  • ammonium nitriles are used as bleach activators in bleaching washes Detergents used. You can et al be used as a dishwasher cleaner,
  • Another problem particularly with automatic dishwashing detergents is the need. in such agents to incorporate corrosion inhibitors for silverware, in particular when the means in More recently, conventional oxygen-based bleaching or oxidizing agents are included.
  • Silver can when cleaning with sulfur-containing substances that are dissolved or dispersed in the rinse water, react, because When cleaning dishes in household dishwashers are leftovers and thus, among other things Mustard, peas, egg and other sulfur-containing compounds such as mercapto amino acids introduced into the rinsing liquor.
  • the much higher temperatures during the mechanical rinsing and the longer contact times with the sulphurous food residues favor the tarnishing of silver compared to manual rinsing.
  • the intensive cleaning process in the dishwasher the silver surface is also completely degreased and thus more sensitive to chemical influences.
  • Such active oxygen bleaching agents become. usually together with bleach activators. especially in modern low alkaline machine dishwashing detergents of the new generation of cleaners are used.
  • builder component complexing agent / dispersant
  • alkali carrier alkali carrier
  • Bleach system bleach and bleach activator combination
  • enzyme and surfactant are usually not only formed in the presence of silver sulfidic, but by the oxidizing attack of intermediately formed peroxides or the active oxygen also oxidic deposits on the silver surfaces.
  • the present invention has the improvement of the oxidation and bleaching action, in particular inorganic Peroxygen compounds at low temperatures below 80 ° C. especially in the temperature range from about 15 ° C to 55 ° C, to the destination.
  • the invention relates to a means for cleaning dishes, which is characterized in that it is 1 wt .-% to 10 wt .-%, in particular 3 wt .-% to 6 wt .-% of a compound of general formula I.
  • Another object of the invention is a means for cleaning dishes, which is characterized in that it is 1 wt .-% to 10 wt .-%, in particular 3 wt .-% to 6 wt .-% of a compound of general formula I.
  • Another object of the invention is a means for cleaning dishes, which is characterized in that it is 1 wt .-% to 10 wt .-%, in particular 3 wt .-% to 6 wt .-% of a compound of general formula I.
  • R 1 is preferably an alkyl group having 1 to 3 C atoms, in particular a methyl group.
  • the anions X - include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, hexafluorophosphate, metho and ethosulfate, chlorate, perchlorate, and the anions of carboxylic acids such as formate, acetate, benzoate or citrate.
  • Methosulfate is - preferred is the use of compounds of the formula in which X is.
  • a dishwashing detergent according to the invention contains the bleach-activating acetonitrile derivative and optionally a peroxygen-containing oxidizing agent, preferably selected from the group comprising organic Peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.
  • the conditions can be widely varied. So come in addition to purely aqueous solutions, mixtures of water and suitable organic solvents as the reaction medium in question.
  • the amounts of peroxygen compounds are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5,000 ppm active oxygen available.
  • the amount of bleach activating acetonitrile derivative used depends on the application from. Depending on the desired degree of activation, 0.00001 mol to 0.25 mol, preferably 0.001 mol to 0.02 moles of activator per mole of peroxygen compound used, but in special cases these limits also be exceeded or fallen below.
  • the cleaning agents of the invention as powdered or tablet-like solids, homogeneous solutions or suspensions may, in principle except the bleach activator used in the invention contain all known and customary in such agents ingredients.
  • the agents according to the invention can in particular builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic Solvents, enzymes. Sequestering agents, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, Foam regulators, additional bleach-enhancing agents, as well as dyes and fragrances.
  • a cleaning agent according to the invention can have abrasive components, in particular from the group comprising quartz flours, wood flours. Plastic flours, chalks and glass microspheres and mixtures thereof. contain. Abrasives are preferably not more than 20% by weight in the detergents according to the invention, in particular from 5% to 15% by weight.
  • a further subject of the invention is a means for mechanically cleaning dishes containing 15 Wt .-% to 70 wt .-%, in particular 20 wt .-% to 60 wt .-% of water-soluble builder component, 5 wt .-% bis 25 wt .-%, in particular 8 wt .-% to 17 wt .-% bleaching agent based on oxygen, in each case based on the total
  • Such an agent is preferably lower alkyl, that is, its 1 weight percent solution a pH of 8 to 11.5, especially from 9 to 11.
  • Alkaliphosphate in the form of their alkaline neutral or acidic sodium or potassium salts may be present.
  • examples of these are trisodium phosphate, tetrasodium diphosphate. disodium, Pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization from 5 to 1000, especially 5 to 50, and mixtures of sodium and potassium salts.
  • Your Amounts can range up to about 55% by weight based on the total agent; are preferred Low alkaline agents according to the invention free of such phosphates.
  • Other possible water-soluble builder components are, for example, organic polymers of native or synthetic origin, especially polycarboxylates, which act as co-builders, especially in hard water regions.
  • polyacrylic acids are suitable and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids.
  • commercial Products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • polymers of native origin include oxidized starches, such as those from international sources Patent Application WO 94/05762, and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, Dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • Preferred builder components include the salts of citric acid, especially sodium citrate.
  • Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the pH adjusted to the compositions according to the invention can also at least proportionally be added to the said co-builder salts corresponding acids are present.
  • alkali perborate mono-abstraction-tetrahydrate is primarily used and / or alkali metal percarbonate and alkali persulfates, persilicates and percarbonates, with sodium being the preferred Alkali metal is.
  • the use of sodium percarbonate has particular advantages in dishwashing detergents, because it has a particularly favorable effect on the corrosion behavior of glasses.
  • the bleaching agent based on oxygen is therefore preferably an alkali metal percarbonate, in particular sodium percarbonate.
  • peroxycarboxylic acids for example dodecanedioic acid or phthalimidopercarboxylic acids, which may optionally be substituted on the aromatic be included.
  • the addition can also small amounts of known bleach stabilizers such as phosphonates, borates or Metaborates and metasilicates and magnesium salts such as magnesium sulfate be useful.
  • bleach-activating acetonitrile derivatives according to formula I known conventional Bleach activators, that is, compounds which under perhydrolysis conditions are aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted Perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the from the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated Sorbitol and mannitol or their mixtures described in European patent application EP 0 5
  • German Patent Application DE 196 16 769 known hydrophilic substituted acylacetals and in the German Patent Application DE 196 16 770 and the international patent application WO 95/14075 Acyllactame described are also preferably used. Also known from German Patent Application DB 44 43 177 Combinations of conventional bleach activators can be used. Such conventional bleach activators are in the usual amount range, preferably in amounts of 0.1 wt .-% to 10 wt .-%, in particular 0.5 wt .-% to 7 wt .-%, based on the total agent included.
  • the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleach catalysts.
  • Suitable transition metal compounds include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salene complexes known from German patent application DE 195 29 905 and their N-analogues known from German patent application DE 196 20 267, which are known from US Pat German Patent Application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl, the described in the German patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium , Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium-ammine complexes known from German patent application DE 196 20 411, the manganese described in German patent application DE 44 16 438, Copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese complex known from European patent application EP 0
  • bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775.
  • Bleach-enhancing transition metal salts and / or complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in conventional amounts, preferably up to 1 wt .-%, in particular of 0.0025 wt % to 0.5 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.
  • Particularly preferred bleach catalyst complexes include cobalt, iron, copper and ruthenium ammine complexes, for example [Co (NH 3 ) 5 Cl] Cl 2 and / or [Co (NH 3 ) 5 NO 2 ] Cl 2 .
  • the machine dishwashing detergents according to the invention preferably contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali metal bicarbonates.
  • Alkali silicates may be present in amounts of up to 40% by weight. based on the total agent, be included.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably completely dispensed with.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight is. Depending on which pH is ultimately desired, the ratio of carbonate used and hydrogen carbonate used varies.
  • compositions according to the invention 20% by weight to 60% by weight are more water-soluble organic builder, in particular alkali citrate, 3% by weight to 20% by weight alkali carbonate and 5% by weight to 40% by weight Alkalidisilicate included.
  • anionic, nonionic and / or amphoteric surfactants in particular low-foaming nonionic surfactants, which serve to better remove greasy soilings, as wetting agents and optionally as granulation aids in the preparation of the cleaning agents.
  • Their amount can be up to 20 wt .-%, in particular up to 10 wt .-% and is preferably in the range of 0.5 wt .-% to 5 wt .-%.
  • extremely low-foam compounds are used in particular in detergents for use in automatic dishwashing processes.
  • C 12 -C 18 -alkylpolyethylenglykol-polypropylene glycol ethers with in each case at to 8 mol ethylene oxide and propylene oxide units in the molecule.
  • surfactants from the family of glucarnides for example alkyl-N-methylglucamides, in which the alkyl moiety preferably originates from a fatty alcohol with the C chain length C 6 -C 14 . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides.
  • silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl-, aminoalkyl- or aryl-substituted triazoles such as Benzotriazole, isocyanuric acid, manganese, cobalt, titanium, zirconium, hafnium, vanadium or cerium salts and / or Complexes in which the metals mentioned are present in one of the oxidation states II, III, IV, V or VI, depending on the metal.
  • the content of silver corrosion inhibitors in compositions according to the invention is preferably in the range of 0.01% by weight.
  • the agents of the invention can enzymes such as proteases, amylases, pullulanases, cutinases and lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purafect® OxP and / or Durazym®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
  • proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purafect® OxP and / or Durazym®
  • amylases such as Termamyl®, Amylase-LT®, Maxamyl®,
  • the optionally used enzymes as for example in the international patent applications WO 92/11347 or WO 94/23005, adsorbed on carriers and / or be embedded in encasing substances, against them Protect premature inactivation. They are preferably present in the detergents according to the invention in quantities up to 2 wt .-%, in particular from 0.1 wt .-% to 1.5 wt .-%, containing, with particular preference against oxidative Degradation stabilized enzymes, such as from International Patent Applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350.
  • the cleaning agents foam too much during use, they can still preferably up to 6 wt .-%, in particular about 0.5 wt .-% to 4 wt .-% of a foam-pressing compound, preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis-fatty acid amides, and other further known commercially available Defoamer be added.
  • a foam-pressing compound preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis-fatty acid amides, and other further known commercially available Defoamer be added.
  • Further optional ingredients in the agents according to the invention are, for example Perfume oils.
  • usable organic solvents include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, Isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and their Mixtures and the derivable from the said classes of compounds ethers.
  • Such water-miscible solvents are preferably not more than 20% by weight, in particular of 1, in the cleaning agents according to the invention Wt .-% to 15 wt .-%, present.
  • the agents of the invention system- and environmentally friendly acids in particular Citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or Adipic acid, but also mineral acids, in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular Ammonium or alkali hydroxides.
  • Such pH regulators are in the inventive compositions preferably not more than 10% by weight, in particular from 0.5% by weight to 6% by weight.
  • Detergents according to the invention in the form of aqueous or other conventional solvent-containing solutions be particularly advantageous by simply mixing the ingredients in substance or as a solution in an automatic mixer can be made.
  • the agents according to the invention are preferably in the form of powdered, granular or tablet-shaped preparations before, in a conventional manner, for example by mixing, granulating, roll compacting and / or by spray-drying the thermally stable components and admixing the more sensitive components, to which in particular enzymes, bleaching agents and the bleach activator are to be expected can be produced.
  • a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 to 1000 g / l can be carried out by a first process step, the builder components with at least a proportion of liquid mixture components mixed with increasing the bulk density of this premix and subsequently - if desired after a Intermediate drying - the other ingredients of the agent, including the bleach catalyst, with the thus obtained Pre-mix united.
  • Detergent cleaning compositions according to the invention can be used both in household dishwashers used in commercial dishwashers. The addition is carried out by hand or by means of suitable metering devices.
  • the application concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.
  • a machine wash program will generally be followed by some intermediate rinse cycles following the cleaning cycle supplemented with clear water and a rinse with a common rinse aid and completed. After drying, the use of compositions according to the invention gives completely clean and hygienic products Respectable dishes.
  • a detergent (V1) for the machine cleaning of dishes containing 45 parts by weight of sodium citrate, 5 parts by weight of sodium carbonate, 30 parts by weight of sodium bicarbonate, each 1 part by weight of protease and amylase granules, 2 wt.
  • the grades of the agents according to the invention given in Table 2 are significantly better than the value for the comparative products V1 and V2 , which contained the standard bleach activator TAED.
  • composition of automatic dishwashing detergent medium additive M1 3 parts by weight of N-methyl-morpholinium-acetonitrile-methosulfate M2 3 parts by weight of N-methyl-morpholinium acetonitrile methosulfate and 0.03 parts by weight of nitropentammine cobalt (III) chloride M3 4 parts by weight of N-methyl-morpholinium-acetonitrile methosulfate M4 4 parts by weight of N-methyl-morpholinium acetonitrile methosulfate and 0.03 parts by weight of nitropentammine cobalt (III) chloride M5 6 parts by weight of N-methyl-morpholinium-acetonitrile methosulfate V2 4 parts by weight TAED Grades for the pad removal medium plaque removal M1 5 M2 7 M3 7 M4 9 M5 9 V1 2 V2 4

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP97951944A 1996-11-29 1997-11-21 Acetonitril-derivate als bleichaktivatoren in reinigungsmitteln Expired - Lifetime EP0944707B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01115441A EP1138754A1 (de) 1996-11-29 1997-11-21 Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19649375 1996-11-29
DE19649375A DE19649375A1 (de) 1996-11-29 1996-11-29 Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
PCT/EP1997/006527 WO1998023719A2 (de) 1996-11-29 1997-11-21 Acetonitril-derivate als bleichaktivatoren in reinigungsmitteln

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP01115441A Division EP1138754A1 (de) 1996-11-29 1997-11-21 Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln

Publications (3)

Publication Number Publication Date
EP0944707A2 EP0944707A2 (de) 1999-09-29
EP0944707B1 EP0944707B1 (de) 2002-02-06
EP0944707B2 true EP0944707B2 (de) 2005-06-01

Family

ID=7813058

Family Applications (2)

Application Number Title Priority Date Filing Date
EP01115441A Ceased EP1138754A1 (de) 1996-11-29 1997-11-21 Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
EP97951944A Expired - Lifetime EP0944707B2 (de) 1996-11-29 1997-11-21 Acetonitril-derivate als bleichaktivatoren in reinigungsmitteln

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP01115441A Ceased EP1138754A1 (de) 1996-11-29 1997-11-21 Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln

Country Status (7)

Country Link
US (1) US6225274B1 (enExample)
EP (2) EP1138754A1 (enExample)
JP (1) JP4097295B2 (enExample)
AT (1) ATE213013T1 (enExample)
DE (2) DE19649375A1 (enExample)
ES (1) ES2172825T5 (enExample)
WO (1) WO1998023719A2 (enExample)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6010994A (en) * 1995-06-07 2000-01-04 The Clorox Company Liquid compositions containing N-alkyl ammonium acetonitrile salts
US7390432B2 (en) 1998-06-30 2008-06-24 Sandia Corporation Enhanced formulations for neutralization of chemical, biological and industrial toxants
US7282470B2 (en) * 2002-07-19 2007-10-16 Sandia Corporation Decontamination formulation with sorbent additive
EP1141211B1 (de) * 1998-12-15 2004-02-25 Henkel Kommanditgesellschaft auf Aktien Teilchenförmig konfektionierte acetonitril-derivate als bleichaktivatoren in festen reinigungsmitteln
DE19908051A1 (de) 1999-02-25 2000-08-31 Henkel Kgaa Verfahren zur Herstellung compoundierter Acetonitril-Derivate
DE19908069A1 (de) * 1999-02-25 2000-08-31 Henkel Kgaa Compoundierte Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
DE19943254A1 (de) 1999-09-10 2001-03-15 Clariant Gmbh Bleichaktive Metallkomplexe
US6214782B1 (en) * 2000-03-24 2001-04-10 Unilever Home & Personal Care, Usa, Division Of Conopco, Inc. Cationic nitriles for providing a silver tarnish benefit in machine dishwashing detergent applications
DE10019877A1 (de) 2000-04-20 2001-10-25 Clariant Gmbh Wasch- und Reinigungsmittel enthaltend bleichaktive Dendrimer-Liganden und deren Metall-Komplexe
DE10038844A1 (de) * 2000-08-04 2002-02-21 Henkel Kgaa Kationischen Bleichaktivator enthaltende Wasch- und Reinigungsmittel
DE10038832A1 (de) * 2000-08-04 2002-03-28 Henkel Kgaa Umhüllte Bleichaktivatoren
DE10038845A1 (de) * 2000-08-04 2002-02-21 Henkel Kgaa Teilchenförmig konfektionierte Acetonitril-Derivate als Bleichaktivatoren in festen Waschmitteln
DE10038180A1 (de) * 2000-08-04 2002-02-14 Reckitt Benckiser Nv Verwendung eines neuartigen Bleichaktivator-Compounds in Geschirrspülmittelzusammensetzungen
DE10057045A1 (de) 2000-11-17 2002-05-23 Clariant Gmbh Teilchenförmige Bleichaktivatoren auf der Basis von Acetonitrilen
DE10064636A1 (de) * 2000-12-22 2002-07-04 Henkel Kgaa Flüssiges Wasch-und/oder Reinigungsmittel
DE10142124A1 (de) 2001-08-30 2003-03-27 Henkel Kgaa Umhüllte Wirkstoffzubereitung für den Einsatz in teilchenförmigen Wasch- und Reinigungsmitteln
DE10159388A1 (de) * 2001-12-04 2003-06-12 Henkel Kgaa Verfahren zur Herstellung von umhüllten Bleichaktivatorgranulaten
DE10159386A1 (de) 2001-12-04 2003-06-12 Henkel Kgaa Verfahren zur Herstellung von Bleichaktivatorgranulaten
DE10211389A1 (de) * 2002-03-15 2003-09-25 Clariant Gmbh Ammoniumnitrile und deren Verwendung als hydrophobe Bleichaktivatoren
JP2006504809A (ja) * 2002-05-02 2006-02-09 ザ プロクター アンド ギャンブル カンパニー 洗剤組成物及びその成分
DE10233832A1 (de) * 2002-07-25 2003-07-17 Henkel Kgaa MGSM mit speziell konfektionierten Bleichaktivatoren
WO2004060856A2 (en) * 2002-12-18 2004-07-22 The Procter & Gamble Company Organic activator

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01198700A (ja) † 1988-02-03 1989-08-10 Kao Corp 自動食器洗浄機用洗剤
EP0790244A1 (de) † 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Ammoniumnitrile und deren Verwendung als Bleichaktivatoren

Family Cites Families (54)

* 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
US4915863A (en) * 1987-08-14 1990-04-10 Kao Corporation Bleaching composition
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
EP0458397B1 (en) 1990-05-21 1997-03-26 Unilever N.V. Bleach activation
GB9011618D0 (en) * 1990-05-24 1990-07-11 Unilever Plc Bleaching composition
GB9012001D0 (en) * 1990-05-30 1990-07-18 Unilever Plc Bleaching composition
DE4041752A1 (de) 1990-12-24 1992-06-25 Henkel Kgaa Enzymzubereitung fuer wasch- und reinigungsmittel
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
EP0544490A1 (en) 1991-11-26 1993-06-02 Unilever Plc Detergent bleach compositions
CA2085642A1 (en) 1991-12-20 1993-06-21 Ronald Hage Bleach activation
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
PT717778E (pt) 1992-07-17 2008-01-16 Genencor Int Serina proteases resistentes a alcalinidade elevada
KR100294361B1 (ko) 1992-07-23 2001-09-17 피아 스타르 돌연변이체알파-아밀라제,세정제,접시세척제,및액화제
DE4228786A1 (de) 1992-08-29 1994-03-03 Henkel Kgaa Geschirrspülmittel mit ausgewähltem Builder-System
DE4232170C2 (de) 1992-09-25 1999-09-16 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
US6297037B1 (en) 1993-02-11 2001-10-02 Christopher C. Barnett Oxidatively stable alpha-amylase
WO1994019445A1 (en) 1993-02-22 1994-09-01 Unilever N.V. Machine dishwashing composition
DE4310506A1 (de) 1993-03-31 1994-10-06 Cognis Bio Umwelt Enzymzubereitung für Wasch- und Reinigungsmittel
DK39093D0 (da) 1993-04-01 1993-04-01 Novo Nordisk As Enzym
DE4325922A1 (de) 1993-08-02 1995-02-09 Henkel Kgaa Silberkorrosionsschutzmittel I
DE4315397A1 (de) 1993-05-08 1994-11-10 Henkel Kgaa Reinigungsmittel mit Verhinderung des Anlaufens von Tafelsilber in Geschirrspülmaschinen
EP0699229A1 (en) 1993-05-20 1996-03-06 The Procter & Gamble Company Bleaching compounds comprising n-acyl caprolactam for use in hand-wash or other low-water cleaning systems
EP0699232B1 (en) 1993-05-20 1999-07-28 The Procter & Gamble Company Bleaching compositions comprising n-acyl caprolactam activators
CA2161214C (en) 1993-05-20 2000-06-27 Alan David Willey Bleaching compounds comprising substituted benzoyl caprolactam bleach activators
US5405413A (en) 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
DK100893D0 (da) 1993-09-09 1993-09-09 Novo Nordisk As Enzym
DE4338922A1 (de) 1993-11-15 1995-05-18 Degussa Aktivatoren für anorganische Persauerstoffverbindungen
ES2133710T3 (es) 1993-11-25 1999-09-16 Warwick Int Group Composiciones blanqueantes.
US5534196A (en) 1993-12-23 1996-07-09 The Procter & Gamble Co. Process for making lactam bleach activator containing particles
CA2187169A1 (en) 1994-04-07 1995-10-19 Gerard Marcel Abel Baillely Bleach compositions comprising metal-containing bleach catalysts
DE4416438A1 (de) 1994-05-10 1995-11-16 Basf Ag Ein- oder mehrkernige Metall-Komplexe und ihre Verwendung als Bleich- und Oxidationskatalysatoren
EP0693550B1 (en) 1994-07-21 2004-06-16 Ciba SC Holding AG Fabric bleaching composition
DE4443177A1 (de) 1994-12-05 1996-06-13 Henkel Kgaa Aktivatormischungen für anorganische Perverbindungen
JPH10513215A (ja) * 1995-02-02 1998-12-15 ザ、プロクター、エンド、ギャンブル、カンパニー コバルト▲ｉｉｉ▼触媒を含む自動皿洗い組成物
US5599781A (en) * 1995-07-27 1997-02-04 Haeggberg; Donna J. Automatic dishwashing detergent having bleach system comprising monopersulfate, cationic bleach activator and perborate or percarbonate
DE19518693A1 (de) 1995-05-22 1996-11-28 Henkel Kgaa Maschinelle Geschirrspülmittel mit Silberkorrosionsschutzmittel
US5792218A (en) * 1995-06-07 1998-08-11 The Clorox Company N-alkyl ammonium acetonitrile activators in dense gas cleaning and method
US5739327A (en) * 1995-06-07 1998-04-14 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US5814242A (en) * 1995-06-07 1998-09-29 The Clorox Company Mixed peroxygen activator compositions
US5888419A (en) * 1995-06-07 1999-03-30 The Clorox Company Granular N-alkyl ammonium acetontrile compositions
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
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
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
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01198700A (ja) † 1988-02-03 1989-08-10 Kao Corp 自動食器洗浄機用洗剤
EP0790244A1 (de) † 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Ammoniumnitrile und deren Verwendung als Bleichaktivatoren

Also Published As

Publication number Publication date
EP1138754A1 (de) 2001-10-04
WO1998023719A2 (de) 1998-06-04
JP2001504883A (ja) 2001-04-10
ATE213013T1 (de) 2002-02-15
DE59706340D1 (de) 2002-03-21
EP0944707B1 (de) 2002-02-06
DE19649375A1 (de) 1998-06-04
ES2172825T5 (es) 2005-12-01
WO1998023719A3 (de) 1998-07-30
JP4097295B2 (ja) 2008-06-11
US6225274B1 (en) 2001-05-01
EP0944707A2 (de) 1999-09-29
ES2172825T3 (es) 2002-10-01

Similar Documents

Publication Publication Date Title
EP0944707B2 (de) Acetonitril-derivate als bleichaktivatoren in reinigungsmitteln
EP2329000B1 (de) Verwendung von mangan-oxalaten als bleichkatalysatoren
EP0912690B1 (de) Katalytisch wirksame aktivatorkomplexe mit n 4?-liganden für persauerstoffverbindungen
EP1445305B1 (de) Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren
EP1225215B1 (de) Verwendung von Übergangsmetallkomplexen mit Oxim-Liganden als Bleichkatalysatoren
EP2329001B1 (de) Bleichkatalysatormischungen bestehend aus mangansalzen und oxalsäure oder deren salze
EP1155110A1 (de) Verfahren zur herstellung compoundierter acetonitril-derivate
DE19709284A1 (de) Katalytisch aktive Wirkstoffkombination zur Verstärkung der Bleichwirkung
EP0832969B1 (de) Katalytisch aktive Wirkstoffkombination zur Verstärkung der Bleichwirkung
EP0846156B1 (de) Reinigungsmittel mit aktivatorkomplexen für persauerstoffverbindungen
WO2000050553A1 (de) Compoundierte acetonitril-derivate als bleichaktivatoren in reinigungsmitteln
DE19713851B4 (de) Verwendung von Komplexen des Molybdäns, Vanadiums oder Wolframs zur Verstärkung der Bleichwirkung
EP1105454A1 (de) Mangankomplexe als katalysatoren für persauerstoffverbindungen zur reinigung von harten oberflächen, insbesondere von geschirr
WO1997036986A1 (de) Reinigungsmittel mit oligoamminaktivatorkomplexen für persauerstoffverbindungen
EP1969112B1 (de) Reinigungsmittel mit bleichkatalytisch aktiven komplexen
EP0864641A1 (de) Verwendung von in Käfigverbindungen eingeschlossenen Übergangsmetallkomplexen zur Verstärkung der Bleichwirkung
EP0845524A2 (de) Verwendung von Wolframaten und Molybdaten zur Verstärkung der Bleichwirkung
DE19649103A1 (de) Reinigungsmittel mit Carbonato-Oligoamminkomplexen
DE19613104A1 (de) Reinigungsmittel mit Oligoamminaktivatorkomplexen für Persauerstoffverbindungen
WO2000075270A1 (de) Herstellung einer bleichkatalytisch aktiven wirkstoffkombination
DE19639599A1 (de) Katalytisch aktive Wirkstoffkombination zur Verstärkung der Bleichwirkung

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: 19990520

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE DE ES FR GB IT NL

17Q First examination report despatched

Effective date: 19991220

APAB Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPE

APAB Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPE

APBJ Interlocutory revision of appeal recorded

Free format text: ORIGINAL CODE: EPIDOS IRAPE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR GB IT NL

REF Corresponds to:

Ref document number: 213013

Country of ref document: AT

Date of ref document: 20020215

Kind code of ref document: T

REF Corresponds to:

Ref document number: 59706340

Country of ref document: DE

Date of ref document: 20020321

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20020502

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2172825

Country of ref document: ES

Kind code of ref document: T3

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: BASF AKTIENGESELLSCHAFT

Effective date: 20021106

NLR1 Nl: opposition has been filed with the epo

Opponent name: BASF AKTIENGESELLSCHAFT

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20050601

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE DE ES FR GB IT NL

NLR2 Nl: decision of opposition

Effective date: 20050601

GBTA Gb: translation of amended ep patent filed (gb section 77(6)(b)/1977)
NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Date of ref document: 20050824

Kind code of ref document: T5

ET3 Fr: translation filed ** decision concerning opposition
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20071104

Year of fee payment: 11

Ref country code: ES

Payment date: 20071219

Year of fee payment: 11

Ref country code: DE

Payment date: 20071115

Year of fee payment: 11

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

Ref country code: AT

Payment date: 20071113

Year of fee payment: 11

Ref country code: IT

Payment date: 20071124

Year of fee payment: 11

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

Ref country code: GB

Payment date: 20071121

Year of fee payment: 11

Ref country code: FR

Payment date: 20071108

Year of fee payment: 11

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

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

Ref country code: BE

Payment date: 20071130

Year of fee payment: 11

BERE Be: lapsed

Owner name: *HENKEL K.G.A.A.

Effective date: 20081130

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

Effective date: 20081121

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

Ref country code: NL

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

Effective date: 20090601

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20090601

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: 20081121

Ref country code: AT

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

Effective date: 20081121

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: 20081130

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

Ref country code: DE

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

Effective date: 20090603

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: 20081121

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20081122

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: 20081122

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110218

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: 20081201