EP1969110B1 - Aerosol cleaner with corrosion-inhibiting action - Google Patents

Aerosol cleaner with corrosion-inhibiting action Download PDF

Info

Publication number
EP1969110B1
EP1969110B1 EP06829763A EP06829763A EP1969110B1 EP 1969110 B1 EP1969110 B1 EP 1969110B1 EP 06829763 A EP06829763 A EP 06829763A EP 06829763 A EP06829763 A EP 06829763A EP 1969110 B1 EP1969110 B1 EP 1969110B1
Authority
EP
European Patent Office
Prior art keywords
aerosol
corrosion
surfactants
use according
acid
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.)
Revoked
Application number
EP06829763A
Other languages
German (de)
French (fr)
Other versions
EP1969110A1 (en
Inventor
Michael Dreja
Daniela Poethkow
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=37836852&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1969110(B1) "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
Publication of EP1969110A1 publication Critical patent/EP1969110A1/en
Application granted granted Critical
Publication of EP1969110B1 publication Critical patent/EP1969110B1/en
Revoked 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0043—For use with aerosol devices
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C11D2111/12—

Definitions

  • the subject of this application is the use of a nanoparticulate colloidal silica as a corrosion inhibitor in aqueous compositions stored in aerosol spray cans.
  • aerosol containers for spraying cleaning agents
  • the use of an aerosol cleaner offers many advantages.
  • the cleaning agent is distributed evenly on the surface of the application, furthermore it can be dosed easily and easily controlled, and the consumption of cleaning agent is lower.
  • a cleaning foam can also be produced.
  • the use of aerosol cleaning foams is particularly advantageous if active ingredients are to be applied in a particularly uniform and finely distributed manner or are to be redistributed or incorporated optically recognizable after application.
  • An example of this is the carpet cleaning, in which aerosol foams are widely used, because a uniform spraying, incorporation and. Drying of the foam and a subsequent suction are required.
  • US 2004/0144406 and WO 98/04 666 offerable spray cleaner for carpets.
  • Aerosol containers are generally made of aluminum or sheet steel. Interior painting can help prevent corrosion. However, the interior painting is expensive to apply and more expensive the manufacturing process. Steel sheets are usually provided with a thin tin coating, which has a higher corrosion barrier against cleaning formulations (especially against chloride ions, including surfactants, and against acids and bases) than the pure steel sheet. However, there is a risk that the tinning is not applied absolutely evenly. In this case, it can lead to defects to so-called pitting. If the tin layer is no longer intact, forms an electrochemical element and a flow of corrosion current at the contact point of both metals, so that a continuous destruction of the steel begins, which can lead to the formation of holes. For this reason, cleaner formulations that are stored in aerosol packaging are added to corrosion inhibitors, see, for example US 5,462,727 ,
  • Common corrosion inhibitors used in amounts of 0.01 to 5 wt .-% for example, alkali metal nitrites and benzoates, borates, alkanolamines and amides, amine compounds such as morpholine, amides or silicones.
  • nitrites and borates are not timely agents due to their chemical irritation; Amines and amides, however, are often not sufficiently effective to prevent corrosion of the aerosol container in the long term.
  • the question arose for an effective, low-irritation corrosion inhibitor which is compatible with common aerosol cleaning formulations.
  • colloidal, particulate silica having particle sizes of 2-50 nm, preferably 5 to 20 nm, in particular 8 to 12 nm, leads to cleaning formulations for permanent inhibition of the corrosion of tin-coated steel sheet aerosol containers, the effect of other, previously known corrosion inhibitors significantly exceeds.
  • This is not limited to carpet cleaners, but can also be used for other aerosol formulations based on water, such as air fresheners, impregnants, furniture care, all-purpose cleaners, deodorants, hair sprays, glass cleaners, sprayable butter, etc. advantageous.
  • the subject of this invention is therefore the use of a nanoparticulate colloidal silica as a corrosion inhibitor in aqueous compositions stored in aerosol spray cans.
  • this corrosion inhibitor is used in carpet cleaners.
  • the intimiditessmitlel can be filled into commercial aerosol containers. Particular preference is given to using containers made of tin-plated steel sheet.
  • the carpet cleaner is used in a carpet cleaning process in which the agent is sprayed evenly on the carpet to be cleaned and optionally incorporated with the aid of a brush or other cleaning aid, then dried and then removed with the vacuum cleaner from the carpet.
  • fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms.
  • the former are particularly preferred for their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them.
  • the oxo alcohols or their derivatives which are obtainable, for example, by the ROELEN's oxo synthesis can also be used correspondingly.
  • alkaline earth metals are mentioned as counter ions for monovalent anions, this means that the alkaline earth metal, of course, only in the half - sufficient for charge balance - amount of substance as the anion is present.
  • Substances which also serve as ingredients of cosmetic products are hereinafter referred to as appropriate according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature.
  • INCI International Nomenclature Cosmetic Ingredient
  • the INCI names are the " International Cosmetic Ingredient Dictionary and Handbook, Seventh Edition (1997 issued by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101, 17 th Street NW, Suite 300, Washington, DC, 20036, USA, and more than 9,000 INCI names and references to more than 37,000 Includes trade names and technical names including associated distributors from over 31 countries
  • the International Cosmetic Ingredient Dictionary and Handbook assigns one or more chemical classes (Chemical Classes) to the ingredients, such as “Polymeric Ethers”, and one or more functions, for example “Surfactants - Cleansing Agents", to which it will be further explained, and where appropriate also referred to below.
  • the indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service. Unless otherwise stated, amounts given are percentages by weight (% by weight) of the total composition. These percentages refer to active contents.
  • a colloidal nanoparticulate silica is used, in particular a colloidal silica sol.
  • Colloidal nanoparticulate silica sols for the purposes of this invention are stable dispersions of amorphous particulate silicon dioxide SiO 2 having particle sizes in the range from 1 to 100 nm. The particle sizes are preferably in the range from 2 to 50 nm, more preferably from 5 to 20 nm, in particular from 8 to 12 nm.
  • an example of a silica sol, which is suitable to be used for the purposes of this invention is that available under the trade name Bindzil ® 30/360 from Akzo silica sol having a particle size of 9 nm.
  • silica sols are Bindzil ® 15/500, 30/220, 40/200 (Akzo), Nyacol ® 215, 830, 1430, 2034DI and Nyacol ® DP5820, DP5480, DP5540 etc.
  • Levasil ® 100/30 , 100F / 30, 100S / 30, 200/30, 200F / 30, 300F / 30, VP 4038, VP 4055 (HC Starck / Bayer) or CAB-O-SPERSE ® PG 001, PG 002 (aqueous dispersion of CAB -O-SIL ®, Cabot), Quartron PL-1, PL-3 (FusoChemical Co.), Köstrosol 0830, 10 30, 1430 (Chemiewerk Bad Köstritz). It can work with the silica sols used also be surface-modified silica treated with sodium aluminate (alumina-modified silica).
  • the carpet cleaning composition advantageously comprises one or more surfactants, preferably those selected from the group consisting of anionic surfactants, nonionic surfactants and mixtures thereof, in amounts of from 0.1 to 10% by weight, preferably from 1 to 5% by weight.
  • surfactants preferably those selected from the group consisting of anionic surfactants, nonionic surfactants and mixtures thereof, in amounts of from 0.1 to 10% by weight, preferably from 1 to 5% by weight.
  • Suitable anionic surfactants are preferably C 8 -C 18 -alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl moiety, C 8 -C 20 -alkanesulfonates, C 10 -C 20 -alkyl sulfates (fatty alcohol sulfates), C 8 -C 18 -alkyl polyglycol ether sulfates (Fatty alcohol ether sulfates) with 2 to 10 ethylene oxide (EO) and / or propylene oxide (PO) units in the ether part and sulfosuccinic mono- and di-C 8 -C 18 -alkyl esters.
  • C 8 -C 18 -alkylbenzenesulfonates in particular having about 12 C atoms in the alkyl moiety
  • C 8 -C 20 -alkanesulfonates C 10 -C 20 -alkyl sulfates (fatty alcohol
  • C 8 -C 18 - ⁇ -olefinsulfonates sulfonated C 8 -C 18 -fatty acids, in particular dodecylbenzenesulfonate, C 8 -C 22 -Carbonklareamidethersulfate, C 8 -C 18 -Alkylpolyglykolethercarboxylate, C 8 -C 18 -N-Acyltauride , C 8 -C 18 -N sarcosinates and C 8 -C 18 -alkyl isethionates or mixtures thereof.
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates and alkyl sulfates also in the form of their corresponding acid, eg dodecylbenzenesulfonic acid.
  • surfactants examples include sodium lauryl sulfate, sodium lauryl ether sulfate with 2 EO, sodium sec-alkanesulfonate having about 15 C atoms, sodium lauroyl sarcosinate or sodium dioctylsulfosuccinate.
  • C 8 -C 18 -alcohol polyglycol ethers ie ethoxylated and / or propoxylated alcohols having 8 to 18 C atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and / or propylene oxide units (PO), C 8 - are especially nonionic surfactants.
  • C 18 -carboxylic acid polyglycol esters having 2 to 15 EO, for example tallow fatty acid + 6-EO esters, ethoxylated fatty acid amides having 12 to 18 C atoms in the fatty acid part and 2 to 8 EO, long-chain amine oxides having 14 to 20 C atoms and long-chain alkylpolyglycosides with 8 to 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units mentioned above.
  • surfactants examples include oleyl-cetyl-alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, cocoalkyldimethylamine oxide or lauryldimethylamine oxide and cocoalkylpolyglucoside with on average 1.4 glucose units.
  • end-capped C 8 -C 18 -alkyl alcohol polyglycol ethers can also be used, ie compounds in which the usually free OH group of the C 8 -C 18 -alkyl alcohol polyglycol ethers has been etherified.
  • Nitrogen-containing surfactants may be present as further nonionic surfactants, for example fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides, the alkyl groups having 10 to 22 C atoms, preferably 12 to 18 C atoms, have.
  • the degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10.
  • the agent according to the invention contains at least one amine oxide.
  • the agent according to the invention may also contain cationic surfactants and / or amphoteric surfactants.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R IV ) (R v ) N + CH 2 COO - , in which R iii is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -Alkyldimethylcarboxymethylbetain and C 11 -C 17 -Alkylamidopropyl-dimethylcarboxymethylbetain.
  • the compositions contain amphoteric surfactants in amounts, based on the composition, of 0 to 10 wt.%.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi) (R vii) (R viii) (R ix) N + X - in which R VI to R ix four identical or different, in particular two long and two short-chain, alkyl radicals and X - are an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • the compositions contain cationic surfactants in amounts, based on the composition, of 0 to 10 wt .-%.
  • the carpet cleaner is free of cationic and amphoteric surfactants.
  • the carpet cleaning composition may preferably further contain one or more water-soluble and / or water-miscible organic solvents.
  • Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C 1-20 hydrocarbons, preferably C 2-15 hydrocarbons, having at least one hydroxyl group and optionally one or more ether functions COC, ie the carbon atom chain interrupting oxygen atoms.
  • Preferred solvents are the - optionally unilaterally etherified with a C 1-6 alkanol - C 2-6 alkylene glycols and poly-C 2-3 alkylene glycol having an average of 1 to 9 identical or different, preferably the same, alkylene glycol groups per molecule as well C 1-6 alcohols.
  • Exemplary solvents are the following compounds named INCI: Alcohol (ethanol), buteth-3, butoxy diglycol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl Alcohol, butylenes glycol, butyloctanol, diethylenes glycol, dimethoxydiglycol, dimethyl ether, dipropylene glycol, ethoxydiglycol, ethoxyethanol, ethyl hexanediol, glycol, hexanediol, 1,2,6-hexanetriol, hexyl alcohol, hexylenes glycol, isobutoxypropanol, isopentyldiol, 3-methoxybutanol , Methoxydiglycol, Methoxyethanol, Methoxyisopropanol, Methoxymethylbutanol, Methoxy PEG-10, Methylal, Methyl Alcohol, Methyl Hexy
  • Preferred solvents which can be used among the glycols and glycol ethers are, for example, butyl glycol (INCI butoxy ethanol, ethylene glycol butyl ether), diethylene glycol, dipropylene glycol or else propylene glycol;
  • the agent according to the invention contains water-soluble and / or water-miscible organic solvents, preferably in amounts of from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, in particular from 1 to 6% by weight.
  • the agent according to the invention may contain further ingredients.
  • these include in particular salts, polymers, builder components; pH adjusters, acids, bases, waxes, foam inhibitors, foam stabilizers, fragrances, preservatives, disinfectants, thickeners, bleaches, color transfer inhibitors, dye fixatives, soil release agents, soil repellent agents, enzymes, silicones, wetting agents, UV stabilizers, Vaccinants, odor killers, anti-mite agents, anti-mosquito agents, anti-allergy agents, antimicrobial agents, antibacterial agents, antistatic agents and mixtures thereof.
  • the cleaning agent may further contain one or more water-soluble, inorganic and / or organic salts.
  • Useful inorganic salts are preferably selected from the group consisting of colorless water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals, alkaline earth metals, aluminum and / or transition metals; Furthermore, ammonium salts can be used. Particularly preferred are halides and sulfates of the alkali metals; Preferably, therefore, the inorganic salt is selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof.
  • the usable organic salts are in particular colorless water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and / or transition metal salts the carboxylic acids.
  • the salts are selected from the group comprising formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.
  • the polymers which can be used in detergents include, in particular, those having soil release or soil repellent properties, but also those which can be used, for example, as thickeners, defoamers or antiallergic active ingredients, and also other polymers which can usually be employed in cleaners.
  • Soil release and soil repellent polymers are, for example, polymers with perfluorinated side-tack, methacrylic homo- and copolymers, polyamines, in particular alkoxylated polyamines, N-vinyl polymers, for example polyvinylpyrrolidones, polycarboxylates, in particular polyacrylates or acrylic acid-maleic acid copolymers, cellulose derivatives or Copolymers of ethylene terephthalate.
  • Polymeric thickeners are the polyelectrolytes thickening polycarboxylates, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, especially heteropolysaccharides, and other conventional thickening polymers.
  • acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers
  • polysaccharides especially heteropolysaccharides, and other conventional thickening polymers.
  • examples of polymeric thickeners are in particular polysaccharide gums such as xanthan gum or guar gum, but also polyacrylates.
  • Further advantageously usable polymers are polyethylene glycols.
  • polymer-surfactant mixtures can be used, as they are offered by various manufacturers.
  • the raw material Akypogene KTS (Kao), a mixture of a Natriumlaurylethercarboxylat and ammonium polyacrylate , which is particularly well suited for filling in aerosol cans, a preferred ingredient.
  • the polymer draws on the carpet fiber and thus reduces the tendency to repellency.
  • the polymer binds the surfactant used, so that it becomes brittle and thus easier to remove with the vacuum cleaner.
  • the agents may contain volatile alkali.
  • ammonia and / or alkanolamines which may contain up to 9 C atoms in the molecule, are used.
  • alkanolamines the ethanolamines are preferred and of these in turn the monoethanolamine.
  • the cleaning agents according to the invention may also contain small amounts of bases.
  • Preferred bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is particularly preferred.
  • Alkali or bases are used primarily to set a pH between 8.5 and 10.5.
  • Alkaline agents may additionally contain carboxylic acids in addition to the volatile alkali.
  • Suitable carboxylic acids having up to 6 carbon atoms, which may be mono-, di- or polycarboxylic acids.
  • suitable carboxylic acids are acetic acid, glycolic acid, lactic acid, citric acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid, of which acetic acid, citric acid and lactic acid are preferably used.
  • the cleaning agent preferably contains one or more propellants ( INCI propellants) usually in an amount of 1 to 80% by weight, preferably 1.5 to 30% by weight, in particular 2 to 10% by weight, particularly preferably 2.5 to 8 wt .-%, most preferably 3 to 6 wt .-%.
  • INCI propellants usually in an amount of 1 to 80% by weight, preferably 1.5 to 30% by weight, in particular 2 to 10% by weight, particularly preferably 2.5 to 8 wt .-%, most preferably 3 to 6 wt .-%.
  • Propellants are usually propellants, in particular liquefied or compressed gases.
  • the choice depends on the product to be sprayed and the field of application.
  • compressed gases such as nitrogen, carbon dioxide or nitrous oxide, which are generally insoluble in the liquid detergent, the operating pressure decreases with each valve actuation.
  • liquefied gases liquefied gases
  • blowing agents are accordingly: butanes, carbon dioxides, dimethyl carbonates, dimethyl ether, ethanes, hydrochlorofluorocarbon 22, hydrochlorofluorocarbon 142b, hydrofluorocarbon 152a, hydrofluorocarbon 134a, hydrofluorocarbon 227ea, isobutanes, isopentanes, nitrogen, nitrous oxides, pentanes, propanes.
  • Chlorofluorocarbons chlorofluorocarbons, CFCs
  • propellant are, however, preferably largely and in particular completely dispensed with because of their harmful effect on the ozone shield of the atmosphere, which protects against hard UV radiation, the so-called ozone layer.
  • blowing agents are liquefied gases.
  • Liquefied gases are gases that can be converted from the gaseous to the liquid state at usually already low pressures and 20 ° C.
  • under liquefied gases are the hydrocarbons propane, propene, butane, butene, isobutane (2-methylpropane), isobutene (2-methylpropene), which are obtained in oil refineries as by-products from distillation and cracking of petroleum and in natural gas treatment during gasoline separation. Isobutylene) and mixtures thereof.
  • the cleaning agent contains propane, butane and / or isobutane as one or more blowing agents, in particular propane and butane, more preferably propane, butane and Isobutane.
  • propane, butane and isobutane contain, based on the mixture, from 23 to 28.5% by weight of propane and in total from 71.5 to 77% by weight of butane and isobutane, in particular from 23 to 28.4% by weight of propane , 0.1 to 5 wt .-% of butane and 71.5 to 76.9 wt .-% of isobutane, for example -25 wt .-% of propane and a total of 75 wt .-% of butane and isobutane.
  • Butane, and mixtures of propane and butane and of propane, butane and isobutane are, for example, under the trade name Drivosol ® by the company. Oxeno (DE) and Degussa-Hüls (DE) available.
  • the agent can be filled in commercial aerosol containers made of aluminum or steel sheet, as they are offered by various manufacturers. However, aerosol containers made of tinned sheet steel are particularly preferably used.
  • the agent is used in a carpet cleaning process.
  • the cleaning agent is first applied by spraying from an aerosol container on the soiled surface. If appropriate, it is then incorporated with the aid of a brush or another suitable for cleaning aid or substrate. Then the agent dries and is finally removed with the vacuum cleaner together with the dirt.
  • a formulation E1 was prepared, filled into aerosol containers and their corrosion resistance checked. The same procedure was used for two comparative formulations V1 and V2 which did not contain colloidal silica.
  • the compositions are given in the table below, wherein the amounts are in wt .-% of the raw material used, based on the composition.
  • raw material E1 V1 V2 lauryl dimethyl 3.3 3.3 3.3 ethanol 5 5 5 Perfume 0.15 0.15 0.15 Colloidal silica 0.3 - - Ether carboxylic acid / acrylate mixture a 11 11 - Acrylic acid / styrene copolymer - - 8.5 Sodium lauryl sarcosinate - - 1 Dest.
  • the three formulations were filled into tin-coated steel cans (tinplate tin d 65 x 240 NI 15 bar, capacity 600 ml) with propane / butane (Drivosol 3.5 bar) as propellant and a storage test under controlled conditions (12 months 20 ° C, 6 months 40 ° C).
  • the containers were opened after 3, 6 and 12 months and examined for corrosion.
  • the doses filled with the formulation E1 had no dezinnation or corrosion in the headspace, in the mantle and in the bottom area.
  • the cans were absolutely bright inside and showed no attack by the contained cleaner.
  • the comparative formulation V1 degeneration and corrosion in the head space as well as the shell and bottom area had to be determined.
  • the comparative formulation V2 did not lead to any corrosion in the head space and the shell and bottom area, however, the cans showed a strong decontamination in the contact area with the formulation.

Abstract

Use of nano-particulate colloidal silica (I) as corrosion inhibitor in aqueous composition, which is stored in aerosol-spray container. Independent claims are included for: (1) aerosol cleaner comprising (I); and (2) a process for cleaning carpet comprising spraying the aerosol cleaner from an aerosol container, and optionally applying, drying and exhausting.

Description

Gegenstand dieser Anmeldung ist die Verwendung eines nanopartikuläre kolloidale Silica als Korrosionsinhibitor in wässrigen Zusammensetzungen, die in Aerosol-Sprühdosen gelagert werden.The subject of this application is the use of a nanoparticulate colloidal silica as a corrosion inhibitor in aqueous compositions stored in aerosol spray cans.

Die Verwendung von Aerosolcontainern ("Sprühdosen") zum Versprühen von Reinigungsmitteln ist heutzutage sehr gebräuchlich. Die Anwendung eines Reinigers in Aerosolform bietet zahlreiche Vorteile. So wird unter anderem das Reinigungsmittel auf der Anwendungsoberfläche gleichmäßig verteilt, weiterhin lässt es sich einfach und gut kontrollierbar dosieren, zudem ist der Verbrauch an Reinigungsmittel geringer. Bei geeigneter Formulierung kann zudem ein Reinigungsschaum erzeugt werden. Der Einsatz von Aerosol-Reinigungsschäumen ist insbesondere dann vorteilhaft, wenn Wirkstoffe besonders gleichmäßig und feinverteilt angewendet werden sollen oder optisch erkennbar nach Anwendung weiterverteilt oder eingearbeitet werden sollen. Ein Beispiel dafür ist die Teppichreinigung, bei der Aerosol-Schäume weit verbreitet sind, weil ein gleichmäßiges Aufsprühen, Einarbeiten und. Eintrocknen des Schaums sowie ein nachträgliches Absaugen erforderlich sind. US 2004/0144406 and WO 98/04 666 offerbaren Sprühreiniger für Teppiche.The use of aerosol containers ("spray cans") for spraying cleaning agents is very common nowadays. The use of an aerosol cleaner offers many advantages. Among other things, the cleaning agent is distributed evenly on the surface of the application, furthermore it can be dosed easily and easily controlled, and the consumption of cleaning agent is lower. With suitable formulation, a cleaning foam can also be produced. The use of aerosol cleaning foams is particularly advantageous if active ingredients are to be applied in a particularly uniform and finely distributed manner or are to be redistributed or incorporated optically recognizable after application. An example of this is the carpet cleaning, in which aerosol foams are widely used, because a uniform spraying, incorporation and. Drying of the foam and a subsequent suction are required. US 2004/0144406 and WO 98/04 666 offerable spray cleaner for carpets.

Ein Problem der Aerosolverpackung stellt jedoch ihre Korrosionsgefahr dar. Aerosolcontainer werden in der Regel aus Aluminium oder Stahlblech gefertigt. Eine Innenlackierung kann helfen, Korrosion zu vermeiden. Die Innenlackierung ist allerdings aufwendig zu applizieren und verteuert den Herstellprozess. Stahlbleche werden meist mit einer dünnen Zinnbeschichtung versehen, die eine höhere Korrosionsbarriere gegen Reinigungsformulierungen (insbesondere gegen Chloridionen, u.a. aus Tensiden, sowie gegen Säuren und Basen) aufweist als das pure Stahlblech. Allerdings besteht die Gefahr, daß die Verzinnung nicht absolut gleichmäßig appliziert ist. In diesem Fall kann es an Fehlstellen zu sogenannter Lochkorrosion kommen. Ist die Zinnschicht nicht mehr intakt, bildet sich an der Kontaktstelle beider Metalle ein elektrochemisches Element und ein Korrosionsstromfluss, so daß eine kontinuierliche Zerstörung des Stahls einsetzt, der bis zur Lochbildung führen kann. Aus diesem Grunde werden Reinigerformulierungen, die in Aerosolverpackungen gelagert werden, Korrosionsinhibitoren zugesetzt, siehe zum Beispiel US 5 462 727 .However, one problem with aerosol packaging is its risk of corrosion. Aerosol containers are generally made of aluminum or sheet steel. Interior painting can help prevent corrosion. However, the interior painting is expensive to apply and more expensive the manufacturing process. Steel sheets are usually provided with a thin tin coating, which has a higher corrosion barrier against cleaning formulations (especially against chloride ions, including surfactants, and against acids and bases) than the pure steel sheet. However, there is a risk that the tinning is not applied absolutely evenly. In this case, it can lead to defects to so-called pitting. If the tin layer is no longer intact, forms an electrochemical element and a flow of corrosion current at the contact point of both metals, so that a continuous destruction of the steel begins, which can lead to the formation of holes. For this reason, cleaner formulations that are stored in aerosol packaging are added to corrosion inhibitors, see, for example US 5,462,727 ,

Gängige Korrosionsinhibitoren, die in Mengen von 0,01 bis 5 Gew.-% eingesetzt werden, sind beispielsweise Alkalimetallnitrite und -benzoate, Borate, Alkanolamine und -amide, Aminverbindungen wie Morpholin, Amide oder auch Silicone. Jedoch sind Nitrite und Borate aufgrund ihrer chemischen Reizwirkung keine zeitgemäßen Wirkstoffe; Amine und Amide sind dagegen häufig nicht ausreichend wirksam, um die Korrosion der Aerosolbehälter langfristig zu verhindern. Somit stellte sich die Frage nach einem wirksamen, reizarmen Korrosionsinhibitor, der kompatibel mit gängigen Aerosol- Reinigungsformulierungen ist.Common corrosion inhibitors used in amounts of 0.01 to 5 wt .-%, for example, alkali metal nitrites and benzoates, borates, alkanolamines and amides, amine compounds such as morpholine, amides or silicones. However, nitrites and borates are not timely agents due to their chemical irritation; Amines and amides, however, are often not sufficiently effective to prevent corrosion of the aerosol container in the long term. Thus, the question arose for an effective, low-irritation corrosion inhibitor, which is compatible with common aerosol cleaning formulations.

Überraschend wurde nun gefunden, daß der Zusatz von kolloidalem, partikulärem Silica mit Partikelgrößen von 2 - 50 nm, vorzugsweise 5 bis 20 nm, insbesondere 8 bis 12 nm, zu Reinigungsformulierungen zur dauerhaften Inhibierung der Korrosion von Zinn-beschichteten Stahlblech-Aerosolcontainern führt, die die Wirkung anderer, bisher bekannter Korrosionsinhibitoren deutlich übertrifft. Dabei ist dies nicht auf Teppichreiniger beschränkt, sondern kann auch für weitere Aerosolformulierungen auf Wasserbasis, beispielsweise Lufterfrischer, Imprägniermittel, Möbelpflege, Allzweckreiniger, Deodorants, Haarsprays, Glasreiniger, sprühfähige Butter usw. vorteilhaft genutzt werden.Surprisingly, it has now been found that the addition of colloidal, particulate silica having particle sizes of 2-50 nm, preferably 5 to 20 nm, in particular 8 to 12 nm, leads to cleaning formulations for permanent inhibition of the corrosion of tin-coated steel sheet aerosol containers, the the effect of other, previously known corrosion inhibitors significantly exceeds. This is not limited to carpet cleaners, but can also be used for other aerosol formulations based on water, such as air fresheners, impregnants, furniture care, all-purpose cleaners, deodorants, hair sprays, glass cleaners, sprayable butter, etc. advantageous.

Gegenstand dieser Erfindung ist daher die Verwendung eines nanopartikulären kolloidalen Silica als Korrosionsinhibitor in wässrigen Zusammensetzungen, die in Aerosol-Sprühdosen gelagert werden.The subject of this invention is therefore the use of a nanoparticulate colloidal silica as a corrosion inhibitor in aqueous compositions stored in aerosol spray cans.

Vorzugsweise wird dieser Korrosionsinhibitor jedoch in Teppichreinigungsmitteln eingesetzt.Preferably, however, this corrosion inhibitor is used in carpet cleaners.

Das Teppichreinigungsmitlel kann in handelsübliche Aerosolcontainer abgefüllt werden. Besonders bevorzugt werden dabei Container aus verzinntem Stahlblech eingesetzt.The Teppichreinigungsmitlel can be filled into commercial aerosol containers. Particular preference is given to using containers made of tin-plated steel sheet.

Das Teppichreinigungsmittel wird in einem Teppichreinigungsverfahren eingesetzt, bei dem das Mittel gleichmäßig auf den zu reinigenden Teppich aufgesprüht und gegebenenfalls mit Hilfe einer Bürste oder eines anderen zur Reinigung geeigneten Hilfsmittels eingearbeitet wird, eintrocknet und anschließend mit dem Staubsauger wieder vom Teppich entfernt wird.The carpet cleaner is used in a carpet cleaning process in which the agent is sprayed evenly on the carpet to be cleaned and optionally incorporated with the aid of a brush or other cleaning aid, then dried and then removed with the vacuum cleaner from the carpet.

Im Rahmen der vorliegenden Erfindung stehen Fettsäuren bzw. Fettalkohole bzw. deren Derivate - soweit nicht anders angegeben - stellvertretend für verzweigte oder unverzweigte Carbonsäuren bzw. Alkohole bzw. deren Derivate mit vorzugsweise 6 bis 22 Kohlenstoffatomen. Erstere sind insbesondere wegen ihrer pflanzlicher Basis als auf nachwachsenden Rohstoffen basierend aus ökologischen Gründen bevorzugt, ohne jedoch die erfindungsgemäße Lehre auf sie zu beschränken. Insbesondere sind auch die beispielsweise nach der ROELENschen Oxo-Synthese erhältlichen Oxo-Alkohole bzw. deren Derivate entsprechend einsetzbar.In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms. The former are particularly preferred for their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them. In particular, the oxo alcohols or their derivatives which are obtainable, for example, by the ROELEN's oxo synthesis can also be used correspondingly.

Wann immer im folgenden Erdalkalimetalle als Gegenionen für einwertige Anionen genannt sind, so bedeutet das, daß das Erdalkalimetall natürlich nur in der halben - zum Ladungsausgleich ausreichenden - Stoffmenge wie das Anion vorliegt.
Stoffe, die auch als Inhaltsstoffe von kosmetischen Mitteln dienen, werden nachfolgend gegebenenfalls gemäß der International Nomenclature Cosmetic Ingredient- (INCI-) Nomenklatur bezeichnet. Chemische Verbindungen tragen eine INCI-Bezeichnung in englischer Sprache, pflanzliche Inhaltsstoffe werden ausschließlich nach Linné in lateinischer Sprache aufgeführt. Sogenannte Trivialnamen wie "Wasser", "Honig" oder "Meersalz" werden ebenfalls in lateinischer Sprache angegeben. Die INCI-Bezeichnungen sind dem " International Cosmetic Ingredient Dictionary and Handbook, Seventh Edition (1997 )" zu entnehmen, das von The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101, 17th Street NW, Suite 300, Washington, DC 20036, U. S. A., herausgegeben wird und mehr als 9.000 INCI-Bezeichnungen sowie Verweise auf mehr als 37.000 Handelsnamen und technische Bezeichnungen einschließlich der zugehörige Distributoren aus über 31 Ländern enthält. Das International Cosmetic Ingredient Dictionary and Handbook ordnet den Inhaltsstoffen eine oder mehrere chemische Klassen (Chemical Classes), beispielsweise "Polymeric Ethers", und eine oder mehrere Funktionen (Functions), beispielsweise "Surfactants - Cleansing Agents", zu, die es wiederum näher erläutert. Auf diese wird nachfolgend gegebenenfalls ebenfalls Bezug genommen.
Die Angabe CAS bedeutet, daß es sich bei der nachfolgenden Zahlenfolge um eine Bezeichnung des Chemical Abstracts Service handelt.
Soweit nicht explizit anders angegeben, beziehen sich angegebene Mengen in Gewichtsprozent (Gew.-%) auf das gesamte Mittel. Dabei beziehen sich diese prozentualen Mengenangaben auf Aktivgehalte.Whenever in the following alkaline earth metals are mentioned as counter ions for monovalent anions, this means that the alkaline earth metal, of course, only in the half - sufficient for charge balance - amount of substance as the anion is present.
Substances which also serve as ingredients of cosmetic products are hereinafter referred to as appropriate according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English, plant ingredients are listed only after Linnaeus in Latin. So-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names are the " International Cosmetic Ingredient Dictionary and Handbook, Seventh Edition (1997 issued by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101, 17 th Street NW, Suite 300, Washington, DC, 20036, USA, and more than 9,000 INCI names and references to more than 37,000 Includes trade names and technical names including associated distributors from over 31 countries The International Cosmetic Ingredient Dictionary and Handbook assigns one or more chemical classes (Chemical Classes) to the ingredients, such as "Polymeric Ethers", and one or more functions, for example "Surfactants - Cleansing Agents", to which it will be further explained, and where appropriate also referred to below.
The indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.
Unless otherwise stated, amounts given are percentages by weight (% by weight) of the total composition. These percentages refer to active contents.

Korrosionsinhibitorcorrosion inhibitor

Als Korrosionsinhibitor in wässrigen Zusammensetzungen, die in Aerosol-Sprühdosen gelagert werden, wird ein kolloidales nanopartikuläres Silica verwendet, insbesondere ein kolloidales Silica-Sol. Kolloidale nanopartikuläre Silica-Sole im Sinne dieser Erfindung sind stabile Dispersionen von amorphem partikulärem Siliciumdioxid SiO2 mit Partikelgrößen im Bereich von 1 bis 100 nm. Vorzugsweise liegen die Teilchengrößen dabei im Bereich 2 bis 50 nm, besonders bevorzugt 5 bis 20 nm, insbesondere 8 bis 12 nm. Ein Beispiel für ein Silica- Sol, welches geeignet ist, im Sinne dieser Erfindung eingesetzt zu werden, ist das unter dem Handelsnamen Bindzil® 30/360 von der Firma Akzo erhältliche Silica- Sol mit einer Partikelgröße von 9 nm. Weitere geeignete Silica-Sole sind Bindzil® 15/500, 30/220, 40/200 (Akzo), Nyacol® 215, 830, 1430, 2034DI sowie Nyacol® DP5820, DP5480, DP5540 etc. (Nyacol Products), Levasil® 100/30, 100F/30, 100S/30, 200/30, 200F/30, 300F/30, VP 4038, VP 4055 (H.C. Starck/ Bayer) oder auch CAB-O-SPERSE® PG 001, PG 002 (wäßrige Dispersionen von CAB-O-SIL®, Cabot), Quartron PL-1, PL-3 (FusoChemical Co.), Köstrosol 0830, 1030, 1430 (Chemiewerk Bad Köstritz). Bei den eingesetzten Silica-Solen kann es sich auch um oberflächenmodifiziertes Silica handeln, das mit Natriumaluminat behandelt wurde (Alumina-modifiziertes Silica).As a corrosion inhibitor in aqueous compositions stored in aerosol spray cans, a colloidal nanoparticulate silica is used, in particular a colloidal silica sol. Colloidal nanoparticulate silica sols for the purposes of this invention are stable dispersions of amorphous particulate silicon dioxide SiO 2 having particle sizes in the range from 1 to 100 nm. The particle sizes are preferably in the range from 2 to 50 nm, more preferably from 5 to 20 nm, in particular from 8 to 12 nm. an example of a silica sol, which is suitable to be used for the purposes of this invention is that available under the trade name Bindzil ® 30/360 from Akzo silica sol having a particle size of 9 nm. Further suitable silica sols are Bindzil ® 15/500, 30/220, 40/200 (Akzo), Nyacol ® 215, 830, 1430, 2034DI and Nyacol ® DP5820, DP5480, DP5540 etc. (Nyacol Products), Levasil ® 100/30 , 100F / 30, 100S / 30, 200/30, 200F / 30, 300F / 30, VP 4038, VP 4055 (HC Starck / Bayer) or CAB-O-SPERSE ® PG 001, PG 002 (aqueous dispersion of CAB -O-SIL ®, Cabot), Quartron PL-1, PL-3 (FusoChemical Co.), Köstrosol 0830, 10 30, 1430 (Chemiewerk Bad Köstritz). It can work with the silica sols used also be surface-modified silica treated with sodium aluminate (alumina-modified silica).

Tensidesurfactants

Das Teppichreinigungsmittel enthält vorteilhafterweise ein oder mehrere Tenside, vorzugsweise solche, die ausgewählt sind aus der Gruppe umfassend anionische Tenside, nichtionische Tenside und Gemische derselben, in Mengen von 0,1 bis 10 Gew.%, vorzugsweise 1 bis 5 Gew.-%.The carpet cleaning composition advantageously comprises one or more surfactants, preferably those selected from the group consisting of anionic surfactants, nonionic surfactants and mixtures thereof, in amounts of from 0.1 to 10% by weight, preferably from 1 to 5% by weight.

Als anionische Tenside eignen sich vorzugsweise C8-C18-Alkylbenzolsulfonate, insbesondere mit etwa 12 C-Atomen im Alkylteil, C8-C20-Alkansulfonate, C10-C20-Alkylsulfate (Fettalkoholsulfate), C8-C18-Alkylpolyglykolethersulfate (Fettalkoholethersulfate) mit 2 bis 10 Ethylenoxid (EO)- und/oder Propylenoxid (PO)-Einheiten im Etherteil sowie Sulfobernsteinsäuremono- und -di-C8-C18-Alkylester. Weiterhin können auch C8-C18-α-Olefinsulfonate, sulfonierte C8-C18-Fettsäuren, insbesondere Dodecylbenzolsulfonat, C8-C22-Carbonsäureamidethersulfate, C8-C18-Alkylpolyglykolethercarboxylate, C8-C18-N-Acyltauride, C8-C18-N-Sarkosinate und C8-C18-Alkylisethionate bzw. deren Mischungen verwendet werden.
Die anionischen Tenside werden vorzugsweise als Natriumsalze eingesetzt, können aber auch als andere Alkali- oder Erdalkalimetallsalze, beispielsweise Magnesiumsalze, sowie in Form von Ammonium- oder Mono-, Di-, Tri- bzw. Tetraalkylammoniumsalzen enthalten sein, im Falle der Sulfonate und Alkylsulfate auch in Form ihrer korrespondierenden Säure, z.B. Dodecylbenzolsulfonsäure.
Beispiele derartiger Tenside sind Natriumlaurylsulfat, Natriumlaurylethersulfat mit 2 EO, Natrium-sec.-Alkansulfonat mit ca. 15 C-Atomen, Natriumlauroylsarcosinat oder auch Natriumdioctylsulfosuccinat.Suitable anionic surfactants are preferably C 8 -C 18 -alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl moiety, C 8 -C 20 -alkanesulfonates, C 10 -C 20 -alkyl sulfates (fatty alcohol sulfates), C 8 -C 18 -alkyl polyglycol ether sulfates (Fatty alcohol ether sulfates) with 2 to 10 ethylene oxide (EO) and / or propylene oxide (PO) units in the ether part and sulfosuccinic mono- and di-C 8 -C 18 -alkyl esters. Furthermore, C 8 -C 18 -α-olefinsulfonates, sulfonated C 8 -C 18 -fatty acids, in particular dodecylbenzenesulfonate, C 8 -C 22 -Carbonsäureamidethersulfate, C 8 -C 18 -Alkylpolyglykolethercarboxylate, C 8 -C 18 -N-Acyltauride , C 8 -C 18 -N sarcosinates and C 8 -C 18 -alkyl isethionates or mixtures thereof.
The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates and alkyl sulfates also in the form of their corresponding acid, eg dodecylbenzenesulfonic acid.
Examples of such surfactants are sodium lauryl sulfate, sodium lauryl ether sulfate with 2 EO, sodium sec-alkanesulfonate having about 15 C atoms, sodium lauroyl sarcosinate or sodium dioctylsulfosuccinate.

Als nichtionische Tenside sind vor allem C8-C18-Alkoholpolyglykolether, d.h. ethoxylierte und/oder propoxylierte Alkohole mit 8 bis 18 C-Atomen im Alkylteil und 2 bis 15 Ethylenoxid- (EO) und/oder Propylenoxideinheiten (PO), C8-C18-Carbonsäurepolyglykolester mit 2 bis 15 EO, beispielsweise Talgfettsäure+6-EO-ester, ethoxylierte Fettsäureamide mit 12 bis 18 C-Atomen im Fettsäureteil und 2 bis 8 EO, langkettige Aminoxide mit 14 bis 20 C-Atomen und langkettige Alkylpolyglycoside mit 8 bis 14 C-Atomen im Alkylteil und 1 bis 3 Glycosideinheiten zu erwähnten. Beispiele derartiger Tenside sind Oleyl-Cetyl-Alkohol mit 5 EO, Nonylphenol mit 10 EO, Laurinsäurediethanolamid, Kokosalkyldimethylaminoxid bzw. Lauryldimethylaminoxid und Kokosalkylpolyglucosid mit im Mittel 1,4 Glucoseeinheiten. Weiterhin können auch endgruppenverschlossene C8-C18-Alkylalkoholpolyglykolether eingesetzt werden, d.h. Verbindungen, in denen die üblicherweise freie OH-Gruppe der C8-C18-Alkylalkoholpolyglykolether verethert ist. Als weitere nichtionische Tenside können stickstoffenthaltende Tenside enthalten sein, z.B. Fettsäurepolyhydroxyamide, beispielsweise Glucamide, und Ethoxylate von Alkylaminen, vicinalen Diolen und/oder Carbonsäureamiden, die Alkylgruppen mit 10 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen, besitzen. Der Ethoxylierungsgrad dieser Verbindungen liegt dabei in der Regel zwischen 1 und 20, vorzugsweise zwischen 3 und 10. Bevorzugt sind Ethanolamid-Derivate von Alkansäuren mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 16 C-Atomen.
In einer besonders bevorzugten Ausführungsform enthält das erfindungsgemäße Mittel mindestens ein Aminoxid.C 8 -C 18 -alcohol polyglycol ethers, ie ethoxylated and / or propoxylated alcohols having 8 to 18 C atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and / or propylene oxide units (PO), C 8 - are especially nonionic surfactants. C 18 -carboxylic acid polyglycol esters having 2 to 15 EO, for example tallow fatty acid + 6-EO esters, ethoxylated fatty acid amides having 12 to 18 C atoms in the fatty acid part and 2 to 8 EO, long-chain amine oxides having 14 to 20 C atoms and long-chain alkylpolyglycosides with 8 to 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units mentioned above. Examples of such surfactants are oleyl-cetyl-alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, cocoalkyldimethylamine oxide or lauryldimethylamine oxide and cocoalkylpolyglucoside with on average 1.4 glucose units. Furthermore, end-capped C 8 -C 18 -alkyl alcohol polyglycol ethers can also be used, ie compounds in which the usually free OH group of the C 8 -C 18 -alkyl alcohol polyglycol ethers has been etherified. Nitrogen-containing surfactants may be present as further nonionic surfactants, for example fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides, the alkyl groups having 10 to 22 C atoms, preferably 12 to 18 C atoms, have. The degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10. Preferred are ethanolamide derivatives of alkanoic acids having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms.
In a particularly preferred embodiment, the agent according to the invention contains at least one amine oxide.

Neben den bisher genannten Tensidtypen kann das erfindungsgemäße Mittel weiterhin auch Kationtenside und/oder amphotere Tenside enthalten.In addition to the previously mentioned types of surfactant, the agent according to the invention may also contain cationic surfactants and / or amphoteric surfactants.

Geeignete Amphotenside sind beispielsweise Betaine der Formel (Riii)(RiV)(Rv)N+CH2COO-, in der Riii einen gegebenenfalls durch Heteroatome oder Heteroatomgruppen unterbrochenen Alkylrest mit 8 bis 25, vorzugsweise 10 bis 21 Kohlenstoffatomen und Riv sowie Rv gleichartige oder verschiedene Alkylreste mit 1 bis 3 Kohlenstoffatomen bedeuten, insbesondere C10-C18-Alkyldimethylcarboxymethylbetain und C11-C17-Alkylamidopropyl-dimethylcarboxymethylbetain. Die Mittel enthalten amphotere Tenside in Mengen, bezogen auf die Zusammensetzung, von 0 bis 10 Gew.%.Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R IV ) (R v ) N + CH 2 COO - , in which R iii is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -Alkyldimethylcarboxymethylbetain and C 11 -C 17 -Alkylamidopropyl-dimethylcarboxymethylbetain. The compositions contain amphoteric surfactants in amounts, based on the composition, of 0 to 10 wt.%.

Geeignete Kationtenside sind u.a. die quartären Ammoniumverbindungen der Formel (Rvi)(Rvii)(Rviii)(Rix)N+ X-, in der Rvi bis Rix für vier gleich- oder verschiedenartige, insbesondere zwei lang- und zwei kurzkettige, Alkylreste und X- für ein Anion, insbesondere ein Halogenidion, stehen, beispielsweise Didecyl-dimethyl-ammoniumchlorid, Alkyl-benzyl-didecyl-ammoniumchlorid und deren Mischungen. Die Mittel enthalten kationische Tenside in Mengen, bezogen auf die Zusammensetzung, von 0 bis 10 Gew.-%.Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi) (R vii) (R viii) (R ix) N + X - in which R VI to R ix four identical or different, in particular two long and two short-chain, alkyl radicals and X - are an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. The compositions contain cationic surfactants in amounts, based on the composition, of 0 to 10 wt .-%.

In einer besonders bevorzugten Ausführungsform ist das Teppichreinigungsmittel jedoch frei von kationischen und amphoteren Tensiden.In a particularly preferred embodiment, however, the carpet cleaner is free of cationic and amphoteric surfactants.

Lösungsmittelsolvent

Das Teppichreinigungsmittel kann vorzugsweise weiterhin ein oder mehrere wasserlösliche und/oder wassermischbare organische Lösungsmittel enthalten. Geeignete Lösungsmittel sind beispielsweise gesättigte oder ungesättigte, vorzugsweise gesättigte, verzweigte oder unverzweigte C1-20-Kohlenwasserstoffe, bevorzugt C2-15-Kohlenwasserstoffe, mit mindestens einer Hydroxygruppe und gegebenenfalls einer oder mehreren Etherfunktionen C-O-C, d.h. die Kohlenstoffatomkette unterbrechenden Sauerstoffatomen. Bevorzugte Lösungsmittel sind die - gegebenenfalls einseitig mit einem C1-6-Alkanol veretherten - C2-6-Alkylenglykole und Poly-C2-3-alkylenglykolether mit durchschnittlich 1 bis 9 gleichen oder verschiedenen, vorzugsweise gleichen, Alkylenglykolgruppen pro Molekül wie auch die C1-6-Alkohole.
Beispielhafte Lösungsmittel sind die folgenden gemäß INCI benannten Verbindungen: Alcohol (Ethanol), Buteth-3, Butoxydiglycol, Butoxyisopropanol, Butoxypropanol, n-Butyl Alcohol, t-Butyl Alcohol, Butylene Glycol, Butyloctanol, Diethylene Glycol, Dimethoxydiglycol, Dimethyl Ether, Dipropylene Glycol, Ethoxydiglycol, Ethoxyethanol, Ethyl Hexanediol, Glycol, Hexanediol, 1,2,6-Hexanetriol, Hexyl Alcohol, Hexylene Glycol, Isobutoxypropanol, Isopentyldiol, 3-Methoxybutanol, Methoxydiglycol, Methoxyethanol, Methoxyisopropanol, Methoxymethylbutanol, Methoxy PEG-10, Methylal, Methyl Alcohol, Methyl Hexyl Ether, Methylpropanediol, Neopentyl Glycol, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-6 Methyl Ether, Pentylene Glycol, PPG-7, PPG-2-Buteth-3, PPG-2 Butyl Ether, PPG-3 Butyl Ether, PPG-2 Methyl Ether, PPG-3 Methyl Ether, PPG-2 Propyl Ether, Propanediol, Propyl Alcohol (n-Propanol), Propylene Glycol, Propylene Glycol Butyl Ether, Propylene Glycol Propyl Ether, Tetrahydrofurfuryl Alcohol, Trimethylhexanol.
Bevorzugt einsetzbare Lösungsmittel unter den Glykolen und Glykolethern sind beispielsweise Butylglykol (INCI Butoxy Ethanol, Ethylene Glycol Butyl Ether), Diethylenglykol, Dipropylenglykol oder auch Propylenglykol; unter den C1-6-Alkoholen werden vorzugsweise Ethanol, n-Propanol, Isopropanol (INCI Isopropyl Alcohol) oder n-Butanol eingesetzt, insbesondere Ethanol.
Das erfindungsgemäße Mittel enthält wasserlösliche und/oder wassermischbare organische Lösungsmittel bevorzugt in Mengen von 0,01 bis 10 Gew.-%, vorzugsweise 0,1 bis 8 Gew.-%, insbesondere 1 bis 6 Gew.-%.The carpet cleaning composition may preferably further contain one or more water-soluble and / or water-miscible organic solvents. Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C 1-20 hydrocarbons, preferably C 2-15 hydrocarbons, having at least one hydroxyl group and optionally one or more ether functions COC, ie the carbon atom chain interrupting oxygen atoms. Preferred solvents are the - optionally unilaterally etherified with a C 1-6 alkanol - C 2-6 alkylene glycols and poly-C 2-3 alkylene glycol having an average of 1 to 9 identical or different, preferably the same, alkylene glycol groups per molecule as well C 1-6 alcohols.
Exemplary solvents are the following compounds named INCI: Alcohol (ethanol), buteth-3, butoxy diglycol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl Alcohol, butylenes glycol, butyloctanol, diethylenes glycol, dimethoxydiglycol, dimethyl ether, dipropylene glycol, ethoxydiglycol, ethoxyethanol, ethyl hexanediol, glycol, hexanediol, 1,2,6-hexanetriol, hexyl alcohol, hexylenes glycol, isobutoxypropanol, isopentyldiol, 3-methoxybutanol , Methoxydiglycol, Methoxyethanol, Methoxyisopropanol, Methoxymethylbutanol, Methoxy PEG-10, Methylal, Methyl Alcohol, Methyl Hexyl Ether, Methylpropanediol, Neopentyl Glycol, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG- 6 methyl ether, pentylene glycol, PPG-7, PPG-2-buteth-3, PPG-2 butyl ether, PPG-3 butyl ether, PPG-2 methyl ether, PPG-3 methyl ether, PPG-2 propyl ether, propanediol , Propyl alcohol (n-propanol), propylene glycol, propylene glycol butyl ether, propylene glycol propyl ether, tetrahydrofurfuryl alcohol, trimethylhexanol.
Preferred solvents which can be used among the glycols and glycol ethers are, for example, butyl glycol (INCI butoxy ethanol, ethylene glycol butyl ether), diethylene glycol, dipropylene glycol or else propylene glycol; Among the C 1-6 alcohols, preference is given to using ethanol, n-propanol, isopropanol (INCI isopropyl alcohol) or n-butanol, in particular ethanol.
The agent according to the invention contains water-soluble and / or water-miscible organic solvents, preferably in amounts of from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, in particular from 1 to 6% by weight.

Neben den bisher genannten kann das erfindungsgemäße Mittel weitere Inhaltsstoffe enthalten. Hierzu zählen insbesondere Salze, Polymere, Builderkomponenten; pH-Stellmittel, Säuren, Basen, Wachse, Schauminhibitoren, Schaumstabilisatoren, Duftstoffe, Konservierungsmittel, Desinfektionsmittel, Verdickungsmittel, Bleichmittel, Farbtransferinhibitoren, Farbfixierer, Soil-Release-Wirkstoffe, Soil-Repellent-Wirkstoffe, Enzyme, Silicone, Netzmittel, UV-Stabilisatoren, Impfagniermittel, Geruchsvernichter, Anti-Milben-Wirkstoffe, Anti-Mücken-Wirkstoffe, Anti-Allergie-Wirkstoffe, antimikrobielle Wirkstoffe, antibakterielle Wirkstoffe, Antistatikmittel sowie Gemische derselben.In addition to the previously mentioned, the agent according to the invention may contain further ingredients. These include in particular salts, polymers, builder components; pH adjusters, acids, bases, waxes, foam inhibitors, foam stabilizers, fragrances, preservatives, disinfectants, thickeners, bleaches, color transfer inhibitors, dye fixatives, soil release agents, soil repellent agents, enzymes, silicones, wetting agents, UV stabilizers, Vaccinants, odor killers, anti-mite agents, anti-mosquito agents, anti-allergy agents, antimicrobial agents, antibacterial agents, antistatic agents and mixtures thereof.

Salzesalts

Das Reinigungsmittel kann weiterhin ein oder mehrere wasserlösliche, anorganische und/oder organische Salze enthalten.
Einsetzbare anorganische Salze sind dabei vorzugsweise ausgewählt aus der Gruppe umfassend farblose wasserlösliche Halogenide, Sulfate, Sulfite, Carbonate, Hydrogencarbonate, Nitrate, Nitrite, Phosphate und/oder Oxide der Alkalimetalle, der Erdalkalimetalle, des Aluminiums und/oder der Übergangsmetalle; weiterhin sind Ammoniumsalze einsetzbar. Besonders bevorzugt sind dabei Halogenide und Sulfate der Alkalimetalle; vorzugsweise ist das anorganische Salz daher ausgewählt aus der Gruppe umfassend Natriumchlorid, Kaliumchlorid, Natriumsulfat, Kaliumsulfat sowie Gemische derselben.
Bei den einsetzbaren organischen Salzen handelt es sich insbesondere um farblose wasserlösliche Alkalimetall-, Erdalkalimetall-, Ammonium-, Aluminium- und/oder Übergangsmetallsalze der Carbonsäuren. Vorzugsweise sind die Salze ausgewählt aus der Gruppe umfassend Formiat, Acetat, Propionat, Citrat, Malat, Tartrat, Succinat, Malonat, Oxalat, Lactat sowie Gemische derselben.The cleaning agent may further contain one or more water-soluble, inorganic and / or organic salts.
Useful inorganic salts are preferably selected from the group consisting of colorless water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals, alkaline earth metals, aluminum and / or transition metals; Furthermore, ammonium salts can be used. Particularly preferred are halides and sulfates of the alkali metals; Preferably, therefore, the inorganic salt is selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof.
The usable organic salts are in particular colorless water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and / or transition metal salts the carboxylic acids. Preferably, the salts are selected from the group comprising formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.

Polymerepolymers

Zu den in Mitteln einsetzbaren Polymeren zählen insbesondere solche mit Soil-Release- oder Soil-Repellent-Eigenschaften, weiterhin aber auch solche, die bespielsweise als Verdickungsmittel, Entschäumer oder Anti-Allergie-Wirkstoffe dienen können, sowie weitere üblicherweise in Reinigungsmitteln einsetzbare Polymere.
Soil-Release- und Soil-Repellent-Polymere sind beispielsweise Polymere mit perfluorierten Seitenkeften, Methacrylsäurehomo-und Copolymere, Polyamine, insbesondere alkoxylierte Polyamine, N-Vinyl-Polymere, beispielsweise Polyvinylpyrrolidone, Polycarboxylate, insbesondere Polyacrylate oder Acrylsäure-Maleinsäure-Copolymere, Cellulosederivate oder Copolymere des Ethylenterephthalats. Polymere Verdickungsmittel sind die als Polyelektrolyte verdickend wirkenden Polycarboxylate, vorzugsweise Homo- und Copolymerisate der Acrylsäure, insbesondere Acrylsäure-Copolymere wie Acrylsäure-Methacrylsäure-Copolymere, und die Polysaccharide, insbesondere Heteropolysaccharide, sowie andere übliche verdickende Polymere. Beispiele für polymere Verdickungsmittel sind insbesondere Polysaccharidgummen wie Xanthan Gum oder Guar Gum, aber, auch Polyacrylate. Weitere vorteilhaft einsetzbare Polymere sind Polyethylenglykole.
Vorteilhaft können auch Polymer-Tensid-Mischungen eingesetzt werden, wie sie von verschiedenen Herstellern feilgeboten werden. So ist beispielsweise der Rohstoff Akypogene KTS (Kao), ein Gemisch aus einem Natriumlaurylethercarboxylat und Ammoniumpolyacrylat, das besonders gut für die Abfüllung in Aerosoldosen geeignet ist, ein bevorzugter Inhaltsstoff. Das Polymer zieht dabei auf die Teppichfaser auf und reduziert so die Wiederanschmutzungsneigung. Zudem bindet das Polymer das eingesetzte Tensid, so daß es spröde wird und sich dadurch leichter mit dem Staubsauger entfernen lässt.The polymers which can be used in detergents include, in particular, those having soil release or soil repellent properties, but also those which can be used, for example, as thickeners, defoamers or antiallergic active ingredients, and also other polymers which can usually be employed in cleaners.
Soil release and soil repellent polymers are, for example, polymers with perfluorinated side-tack, methacrylic homo- and copolymers, polyamines, in particular alkoxylated polyamines, N-vinyl polymers, for example polyvinylpyrrolidones, polycarboxylates, in particular polyacrylates or acrylic acid-maleic acid copolymers, cellulose derivatives or Copolymers of ethylene terephthalate. Polymeric thickeners are the polyelectrolytes thickening polycarboxylates, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, especially heteropolysaccharides, and other conventional thickening polymers. Examples of polymeric thickeners are in particular polysaccharide gums such as xanthan gum or guar gum, but also polyacrylates. Further advantageously usable polymers are polyethylene glycols.
Advantageously, polymer-surfactant mixtures can be used, as they are offered by various manufacturers. Thus, for example, the raw material Akypogene KTS (Kao), a mixture of a Natriumlaurylethercarboxylat and ammonium polyacrylate , which is particularly well suited for filling in aerosol cans, a preferred ingredient. The polymer draws on the carpet fiber and thus reduces the tendency to repellency. In addition, the polymer binds the surfactant used, so that it becomes brittle and thus easier to remove with the vacuum cleaner.

Flüchtiges Alkali; BasenVolatile alkali; bases

Weiterhin können die Mittel flüchtiges Alkali enthalten. Als solches werden Ammoniak und/oder Alkanolamine, die bis zu 9 C-Atome im Molekül enthalten können, verwendet. Als Alkanolamine werden die Ethanolamine bevorzugt und von diesen wiederum das Monoethanolamin. Daneben können die erfindungsgemäßen Reinigungsmittel auch geringe Mengen an Basen enthalten. Bevorzugte Basen stammen aus der Gruppe der Alkali- und Erdalkalimetallhydroxide und -carbonate, insbesondere der Alkalimetallhydroxide, von denen Kaliumhydroxid und vor allem Natriumhydroxid besonders bevorzugt ist. Alkali bzw. Basen dienen vor allem auch zur Einstellung eines pH-Wertes zwischen 8,5 und 10,5.Furthermore, the agents may contain volatile alkali. As such, ammonia and / or alkanolamines, which may contain up to 9 C atoms in the molecule, are used. As alkanolamines, the ethanolamines are preferred and of these in turn the monoethanolamine. In addition, the cleaning agents according to the invention may also contain small amounts of bases. Preferred bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is particularly preferred. Alkali or bases are used primarily to set a pH between 8.5 and 10.5.

Säurenacids

Alkalische Mittel können neben dem flüchtigen Alkali zusätzlich Carbonsäuren enthalten. Geeignet sind Carbonsäuren mit bis zu 6 C-Atomen, wobei es sich um Mono-, Di- oder Polycarbonsäuren handeln kann. Beispiele geeigneter Carbonsäuren sind Essigsäure, Glykolsäure, Milchsäure, Zitronensäure, Bernsteinsäure, Adipinsäure, Apfelsäure, Weinsäure und Gluconsäure, von denen vorzugsweise Essigsäure, Zitronensäure und Milchsäure verwendet werden.Alkaline agents may additionally contain carboxylic acids in addition to the volatile alkali. Suitable carboxylic acids having up to 6 carbon atoms, which may be mono-, di- or polycarboxylic acids. Examples of suitable carboxylic acids are acetic acid, glycolic acid, lactic acid, citric acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid, of which acetic acid, citric acid and lactic acid are preferably used.

Treibmittelpropellant

Das Reinigungsmittel enthält vorzugsweise ein oder mehrere Treibmittel (INCI Propellants) üblicherweise in einer Menge von 1 bis 80 Gew.%, vorzugsweise 1,5 bis 30 Gew.-%, insbesondere 2 bis 10 Gew.-%, besonders bevorzugt 2,5 bis 8 Gew.-%, äußerst bevorzugt 3 bis 6 Gew.-%.The cleaning agent preferably contains one or more propellants ( INCI propellants) usually in an amount of 1 to 80% by weight, preferably 1.5 to 30% by weight, in particular 2 to 10% by weight, particularly preferably 2.5 to 8 wt .-%, most preferably 3 to 6 wt .-%.

Treibmittel sind üblicherweise Treibgase, insbesondere verflüssigte oder komprimierte Gase. Die Wahl richtet sich nach dem zu versprühenden Produkt und dem Einsatzgebiet. Bei der Verwendung von komprimierten Gasen wie Stickstoff, Kohlendioxid oder Distickstoffoxid, die im allgemeinen in dem flüssigen Reinigungsmittel unlöslich sind, sinkt der Betriebsdruck mit jeder Ventilbetätigung. Im Reinigungsmittel lösliche oder selbst als Lösungsmittel wirkende verflüssigte Gase (Flüssiggase) als Treibmittel bieten den Vorteil gleich bleibenden Betriebsdruck und gleichmäßiger Verteilung, denn an der Luft verdampft das Treibmittel und nimmt dabei ein mehrhundertfaches Volumen ein.Propellants are usually propellants, in particular liquefied or compressed gases. The choice depends on the product to be sprayed and the field of application. When using compressed gases such as nitrogen, carbon dioxide or nitrous oxide, which are generally insoluble in the liquid detergent, the operating pressure decreases with each valve actuation. In the detergent soluble or even acting as a solvent liquefied gases (liquefied gases) as a propellant offer the advantage of constant operating pressure and uniform distribution, because in the air evaporates the propellant and thereby takes up a hundred-fold volume.

Geeignet sind demgemäß folgende gemäß INCI bezeichnete Treibmittel: Butane, Carbon Dioxide, Dimethyl Carbonate, Dimethyl Ether, Ethane, Hydrochlorofluorocarbon 22, Hydrochlorofluorocarbon 142b, Hydrofluorocarbon 152a, Hydrofluorocarbon 134a, Hydrofluorocarbon 227ea, Isobutane, Isopentane, Nitrogen, Nitrous Oxide, Pentane, Propane.According to INCI suitable blowing agents are accordingly: butanes, carbon dioxides, dimethyl carbonates, dimethyl ether, ethanes, hydrochlorofluorocarbon 22, hydrochlorofluorocarbon 142b, hydrofluorocarbon 152a, hydrofluorocarbon 134a, hydrofluorocarbon 227ea, isobutanes, isopentanes, nitrogen, nitrous oxides, pentanes, propanes.

Auf Chlorfluorkohlenstoffe (Fluorchlorkohlenwasserstoffe, FCKW) als Treibmittel wird jedoch wegen ihrer schädlichen Wirkung auf den - vor harter UV-Strahlung schützenden - Ozon-Schild der Atmosphäre, die sogenannte Ozon-Schicht, vorzugsweise weitgehend und insbesondere vollständig verzichtet.Chlorofluorocarbons (chlorofluorocarbons, CFCs) as propellant are, however, preferably largely and in particular completely dispensed with because of their harmful effect on the ozone shield of the atmosphere, which protects against hard UV radiation, the so-called ozone layer.

Bevorzugte Treibmittel sind Flüssiggase. Flüssiggase sind Gase, die bei meist schon geringen Drücken und 20 °C vom gasförmigen in den flüssigen Zustand übergeführt werden können. Insbesondere werden unter Flüssiggasen jedoch die - in Ölraffinerien als Nebenprodukte bei Destillation und Kracken von Erdöl sowie in der Erdgas-Aufbereitung bei der Benzinabscheidung anfallenden - Kohlenwasserstoffe Propan, Propen, Butan, Buten, Isobutan (2-Methylpropan), Isobuten (2-Methylpropen, Isobutylen) und deren Gemische verstanden.Preferred blowing agents are liquefied gases. Liquefied gases are gases that can be converted from the gaseous to the liquid state at usually already low pressures and 20 ° C. In particular, under liquefied gases, however, are the hydrocarbons propane, propene, butane, butene, isobutane (2-methylpropane), isobutene (2-methylpropene), which are obtained in oil refineries as by-products from distillation and cracking of petroleum and in natural gas treatment during gasoline separation. Isobutylene) and mixtures thereof.

Besonders bevorzugt enthält das Reinigungsmittel als ein oder mehrere Treibmittel Propan, Butan und/oder Isobutan, insbesondere Propan und Butan, äußerst bevorzugt Propan, Butan und Isobutan. Bevorzugte Mischungen von Propan, Butan und Isobutan enthalten, bezogen auf die Mischung, 23 bis 28,5 Gew.-% Propan sowie insgesamt 71,5 bis 77 Gew.-% Butan und Isobutan, insbesondere 23 bis 28,4 Gew.% Propan, 0,1 bis 5 Gew.-% Butan und 71,5 bis 76,9 Gew.-% Isobutan, beispielsweise-25 Gew.-% Propan sowie insgesamt 75 Gew.-% Butan und Isobutan. Butan, und Mischungen von Propan und Butan sowie von Propan, Butan und Isobutan sind beispielsweise unter dem Handelsnamen Drivosol ® von der Fa. Oxeno (DE) bzw. Degussa-Hüls (DE) erhällich.Particularly preferably, the cleaning agent contains propane, butane and / or isobutane as one or more blowing agents, in particular propane and butane, more preferably propane, butane and Isobutane. Preferred mixtures of propane, butane and isobutane contain, based on the mixture, from 23 to 28.5% by weight of propane and in total from 71.5 to 77% by weight of butane and isobutane, in particular from 23 to 28.4% by weight of propane , 0.1 to 5 wt .-% of butane and 71.5 to 76.9 wt .-% of isobutane, for example -25 wt .-% of propane and a total of 75 wt .-% of butane and isobutane. Butane, and mixtures of propane and butane and of propane, butane and isobutane are, for example, under the trade name Drivosol ® by the company. Oxeno (DE) and Degussa-Hüls (DE) available.

Aerosolbehälteraerosol container

Das Mittel kann in handelsübliche Aerosolcontainer aus Aluminium oder Stahlblech abgefüllt werden, wie sie von verschiedenen Herstellern feilgeboten werden. Besonders bevorzugt werden jedoch Aerosolcontainer aus verzinntem Stahlblech eingesetzt.The agent can be filled in commercial aerosol containers made of aluminum or steel sheet, as they are offered by various manufacturers. However, aerosol containers made of tinned sheet steel are particularly preferably used.

Reinigungsverfahrencleaning process

Das Mittel wird in einem Teppichreinigungsverfahren verwendet. Hierzu wird zunächst das Reinigungsmittel durch Versprühen aus einem Aerosolbehälter auf die verschmutzte Oberfläche aufgetragen. Gegebenenfalls wird es sodann mit Hilfe einer Bürste oder eines anderen zur Reinigung geeigneten Hilfsmittels oder Substrates eingearbeitet. Anschließend trocknet das Mittel ein und wird schließlich mit dem Staubsauger mitsamt der Verschmutzung entfernt.The agent is used in a carpet cleaning process. For this purpose, the cleaning agent is first applied by spraying from an aerosol container on the soiled surface. If appropriate, it is then incorporated with the aid of a brush or another suitable for cleaning aid or substrate. Then the agent dries and is finally removed with the vacuum cleaner together with the dirt.

Ausführungsbeispiel:Embodiment:

Es wurde eine Formulierung E1 hergestellt, in Aerosolbehälter abgefüllt und deren Korrosionsbeständigkeit überprüft. Mit zwei Vergleichsformulierungen V1 und V2, die kein kolloidales Silica enthielten, wurde ebenso verfahren. Die Zusammensetzungen sind in der nachfolgenden Tabelle wiedergegeben, wobei die Mengenangaben in Gew.-% des eingesetzten Rohstoffs, bezogen auf die Zusammensetzung, sind. Rohstoff E1 V1 V2 Lauryldimethylaminoxid 3,3 3,3 3,3 Ethanol 5 5 5 Parfüm 0,15 0,15 0,15 Kolloidales Silica 0,3 -- -- Ethercarbonsäure/Acrylat-Gemischa 11 11 -- Acrylsäure/Styrol-Copolymer -- -- 8,5 Natrium-Laurylsarcosinat -- -- 1 Dest. Wasser ad 100 ad 100 ad 100 pH (mit NaOH eingestellt) 9,4 9,4 9,4 a: Mischung aus Laurylpolyglycolethercarbonsäure-Natriumsalz und Acrylat-Copolymer, beispielsweise Akypogene KTS ® ex Rhodia A formulation E1 was prepared, filled into aerosol containers and their corrosion resistance checked. The same procedure was used for two comparative formulations V1 and V2 which did not contain colloidal silica. The compositions are given in the table below, wherein the amounts are in wt .-% of the raw material used, based on the composition. raw material E1 V1 V2 lauryl dimethyl 3.3 3.3 3.3 ethanol 5 5 5 Perfume 0.15 0.15 0.15 Colloidal silica 0.3 - - Ether carboxylic acid / acrylate mixture a 11 11 - Acrylic acid / styrene copolymer - - 8.5 Sodium lauryl sarcosinate - - 1 Dest. Water ad 100 ad 100 ad 100 pH (adjusted with NaOH) 9.4 9.4 9.4 a: Mixture of lauryl polyglycol ether carboxylic acid sodium salt and acrylate copolymer, for example Akypogene KTS® ex Rhodia

Die drei Rezepturen wurden in zinnbeschichtete Stahldosen (Weissblech-Dose d 65 x 240 NI 15 bar, Inhalt 600 ml) mit Propan/Butan (Drivosol 3.5 bar) als Treibmittel abgefüllt und einem Lagertest unter kontrollierten Bedingungen (12 Monate 20°C, 6 Monate 40°C) unterzogen. Die Container wurden nach 3, 6 und 12 Monaten geöffnet und auf Korrosion hin untersucht.The three formulations were filled into tin-coated steel cans (tinplate tin d 65 x 240 NI 15 bar, capacity 600 ml) with propane / butane (Drivosol 3.5 bar) as propellant and a storage test under controlled conditions (12 months 20 ° C, 6 months 40 ° C). The containers were opened after 3, 6 and 12 months and examined for corrosion.

Dabei konnte festgestellt werden, daß die mit der Rezeptur E1 befüllten Dosen keine Entzinnung oder Korrosion im Kopfraum, im Mantel und im Bodenbereich aufwiesen. Die Dosen waren von innen absolut blank und zeigten keinen Angriff durch den enthaltenen Reiniger.
Bei mit der Vergleichsrezeptur V1 befüllten Dosen mussten dagegen Entzinnung und Korrosion im Kopfraum sowie Mantel und Bodenbereich festgestellt werden. Die Vergleichsrezeptur V2 führte zwar zu keiner Korrosion im Kopfraum sowie Mantel und Bodenbereich, jedoch wiesen die Dosen eine starke Entzinnung im Kontaktbereich mit der Rezeptur auf.It was found that the doses filled with the formulation E1 had no dezinnation or corrosion in the headspace, in the mantle and in the bottom area. The cans were absolutely bright inside and showed no attack by the contained cleaner.
On the other hand, in the case of doses filled with the comparative formulation V1, degeneration and corrosion in the head space as well as the shell and bottom area had to be determined. Although the comparative formulation V2 did not lead to any corrosion in the head space and the shell and bottom area, however, the cans showed a strong decontamination in the contact area with the formulation.

Claims (7)

  1. The use of a nanoparticulate colloidal silica as an inhibitor of corrosion in aqueous compositions which are stored in aerosol spray cans.
  2. The use according to claim 1, wherein as for the aqueous composition, this is a carpet cleaning agent.
  3. The use according to claim 2, characterized in that the silica has a particle size from 2 to 50 nm, preferably 5 to 20 nm, in particular 8 to 12 nm.
  4. The use according to one of claims 2 and 3, characterized in that the carpet cleaning agent contains one or more surfactants in amounts from 0 to 10% by weight, preferably from 1 to 5% by weight.
  5. The use according to claim 4, characterized in that the surfactants are preferably selected from the group comprising anionic surfactants, non-ionic surfactants or mixtures thereof.
  6. The use according to one of claims 2 to 5, characterized in that the carpet cleaning agent further contains one or more water-soluble and/or water-miscible solvents.
  7. The use according to one of claims 2 to 6, characterized in that one or more propellants are added to the carpet cleaning agent, preferably, propane and/or butane.
EP06829763A 2006-01-02 2006-12-20 Aerosol cleaner with corrosion-inhibiting action Revoked EP1969110B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006000691A DE102006000691A1 (en) 2006-01-02 2006-01-02 Use of nano-particulate colloidal silica as corrosion inhibitor in e.g. aqueous compositions, aerosol on water basis, furniture care, general-purpose cleaner, deodorants, hair spray and glass cleaner
PCT/EP2006/012282 WO2007076930A1 (en) 2006-01-02 2006-12-20 Aerosol cleaner with corrosion-inhibiting action

Publications (2)

Publication Number Publication Date
EP1969110A1 EP1969110A1 (en) 2008-09-17
EP1969110B1 true EP1969110B1 (en) 2012-02-22

Family

ID=37836852

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06829763A Revoked EP1969110B1 (en) 2006-01-02 2006-12-20 Aerosol cleaner with corrosion-inhibiting action

Country Status (5)

Country Link
US (1) US20090018044A1 (en)
EP (1) EP1969110B1 (en)
AT (1) ATE546514T1 (en)
DE (1) DE102006000691A1 (en)
WO (1) WO2007076930A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8178078B2 (en) 2008-06-13 2012-05-15 S.C. Johnson & Son, Inc. Compositions containing a solvated active agent suitable for dispensing as a compressed gas aerosol
US8287841B2 (en) 2010-06-18 2012-10-16 S.C. Johnson & Son, Inc. Aerosol odor eliminating compositions containing alkylene glycol(s)
US8927474B2 (en) 2012-03-16 2015-01-06 S.C. Johnson & Son, Inc. Compressed gas aerosol composition in steel can
US9237216B2 (en) * 2013-03-11 2016-01-12 Intel Corporation Techniques for wirelessly docking to a device
US10398633B2 (en) 2014-10-27 2019-09-03 Conopco, Inc. Anhydrous antiperspirant compositions
EP3370831B1 (en) 2015-11-06 2022-03-23 Unilever IP Holdings B.V. Aerosol antiperspirant product
MX367556B (en) 2015-11-06 2019-08-27 Unilever Nv Antiperspirant compositions.
WO2017076836A1 (en) 2015-11-06 2017-05-11 Unilever Plc Aerosol antiperspirant product
US9856442B1 (en) * 2016-07-24 2018-01-02 Antonio Philippe Anselmo Windshield washer preparation and a method to make the preparation

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625890A (en) * 1969-06-03 1971-12-07 Johnson & Son Inc S C Processes and compositions for the treatment of textile materials
DE2110750A1 (en) * 1970-03-17 1971-10-07 Colgate Palmolive Co Carpet cleaning agent and process for its manufacture
US4482662A (en) * 1982-07-26 1984-11-13 Plasti-Kote Company, Inc. Water-soluble aerosol paint compositions
US4544578A (en) * 1983-11-23 1985-10-01 Chem-Pak, Inc. Method of touching up surface-blemished matt-finished surface grained colored molded plastic parts
US4661556A (en) * 1985-05-24 1987-04-28 Dow Corning Corporation Method of producing reinforced aqueous emulsion of polydiorganosiloxane
US5374434B1 (en) * 1991-11-04 1999-01-19 Creative Products Inc Food release compositions
US5462727A (en) * 1993-02-02 1995-10-31 Dowbrands L.P. Composition for inhibition of corrosion in galvanized steel cans
GB2315783B (en) * 1996-07-27 2000-08-23 Reckitt & Colman Inc Cleaning composition imparting water and oil repellency
AU3393797A (en) * 1996-07-29 1998-02-20 Clorox Company, The Aerosol carpet cleaner
US5945085A (en) * 1997-06-19 1999-08-31 Church & Dwight Co., Inc. Aerosol deodorant-antiperspirant product
GB9925439D0 (en) * 1999-10-27 1999-12-29 Unilever Plc Hair treatment compositions
US20020028288A1 (en) * 2000-06-14 2002-03-07 The Procter & Gamble Company Long lasting coatings for modifying hard surfaces and processes for applying the same
EP1356152A2 (en) * 2001-01-30 2003-10-29 The Procter & Gamble Company Coating compositions for modifying surfaces
US7094842B2 (en) * 2002-01-04 2006-08-22 L'oreal Composition containing a silicone copolymer and an AMPS-like polymer and/or organic powder
US20030216488A1 (en) * 2002-04-18 2003-11-20 The Procter & Gamble Company Compositions comprising a dispersant and microcapsules containing an active material
DE10248583A1 (en) * 2002-10-17 2004-04-29 Nanogate Technologies Gmbh Textile treatment agents
US20040144406A1 (en) * 2003-01-16 2004-07-29 Aram Garabedian Dry aerosol carpet cleaning process
GB0304508D0 (en) * 2003-02-27 2003-04-02 Unilever Plc Antiperspirant actives and compositions
US7459146B2 (en) * 2003-05-30 2008-12-02 3M Innovative Properties Company Stabilized aerosol dispersions
US20050065238A1 (en) * 2003-09-23 2005-03-24 Lark John C. Encapsulated nanoparticles, products containing the same, and methods for using the same
US7678367B2 (en) * 2003-10-16 2010-03-16 Kimberly-Clark Worldwide, Inc. Method for reducing odor using metal-modified particles
US20050281806A1 (en) * 2004-06-16 2005-12-22 Collegium Pharmaceutical, Inc., Delaware Compositions for topical enzymatic debridement

Also Published As

Publication number Publication date
DE102006000691A1 (en) 2007-07-05
WO2007076930A1 (en) 2007-07-12
EP1969110A1 (en) 2008-09-17
ATE546514T1 (en) 2012-03-15
US20090018044A1 (en) 2009-01-15

Similar Documents

Publication Publication Date Title
EP1969110B1 (en) Aerosol cleaner with corrosion-inhibiting action
EP1924678A1 (en) Cleanser for hard surfaces
DE60106272T2 (en) CLEANING COMPOSITIONS
EP1280878B1 (en) Use of nanoscale particles for improving dirt removal
DE60031309T2 (en) CLEANING SUPPLIES
DE10304331B4 (en) Enzymatic removal of biofilms on household surfaces
MX2007011574A (en) Surface treatment.
PT1463795E (en) Cleaning wipe
EP1122302A1 (en) Treatment of soiled textiles
EP2088186A1 (en) Multi-component thin-to-thick system
WO2007082685A1 (en) Sprayable all-purpose cleaner
EP3532586B1 (en) Disinfectant cleaning composition with quaternary ammonium hydroxycarboxylate salt
WO2018080835A1 (en) Disinfectant cleaning composition with quaternary amine ionic liquid
DE102004063765A1 (en) Foam-reinforced cleaner
CN109477039B (en) Defoaming effect enhancer and foamable detergent composition containing the same
WO2008107033A1 (en) Glass cleaner
WO2014012869A1 (en) Stable, liquid detergent with anti-redeposition action
DE60209647T2 (en) Cleaning Wipes
CA3168855A1 (en) Oven cleaning compositions and methods of making and using same
DE19962885A1 (en) Detergent tablets with improved disintegration properties
EP2414495B1 (en) Cleaning agent for floors
WO2004055143A2 (en) Single-dose plastic container provided with cleaning agent for directly removing dirt
DE102006009138A1 (en) Detergent for removing greasy or oily soil and cleaning and conditioning hard surface, e.g. washing machine or automatic dishwasher contains nonionic surfactant mixture of (poly)alkylene oxide mono- or di-ether and amine oxide
WO2005090539A1 (en) Composition for producing ph jump
EP4214300B1 (en) A hard surface cleaning composition

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: 20080405

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20091109

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

DAX Request for extension of the european patent (deleted)
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 HU IE IS IT LI LT LU LV MC NL 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

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 546514

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120315

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: 502006011021

Country of ref document: DE

Effective date: 20120419

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120222

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20120222

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

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: 20120622

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: 20120222

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: 20120622

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: 20120222

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: 20120523

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: 20120222

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: 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: 20120222

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

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: 20120222

Ref country code: PL

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: 20120222

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: 20120222

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: 20120222

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: 20120222

Ref country code: SE

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: 20120222

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: 20120222

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: 20120222

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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: 20120222

Ref country code: IT

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: 20120222

26 Opposition filed

Opponent name: RECKITT BENCKISER (UK) LIMITED

Effective date: 20121116

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502006011021

Country of ref document: DE

Effective date: 20121116

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120602

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20121231

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

Ref country code: MC

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

Effective date: 20121231

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: 20120522

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 20121220

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: 20121231

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

Ref country code: CH

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

Effective date: 20121231

Ref country code: LI

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

Effective date: 20121231

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: 20121220

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 546514

Country of ref document: AT

Kind code of ref document: T

Effective date: 20121220

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120222

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: 20121220

Ref country code: LU

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

Effective date: 20121220

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: 20061220

REG Reference to a national code

Ref country code: DE

Ref legal event code: R064

Ref document number: 502006011021

Country of ref document: DE

Ref country code: DE

Ref legal event code: R103

Ref document number: 502006011021

Country of ref document: DE

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

Ref country code: DE

Payment date: 20141216

Year of fee payment: 9

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

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

Ref country code: FR

Payment date: 20141208

Year of fee payment: 9

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20141209

REG Reference to a national code

Ref country code: DE

Ref legal event code: R107

Ref document number: 502006011021

Country of ref document: DE