EP2470635B1 - Composition nettoyante pour surfaces dures - Google Patents

Composition nettoyante pour surfaces dures Download PDF

Info

Publication number
EP2470635B1
EP2470635B1 EP10759958.1A EP10759958A EP2470635B1 EP 2470635 B1 EP2470635 B1 EP 2470635B1 EP 10759958 A EP10759958 A EP 10759958A EP 2470635 B1 EP2470635 B1 EP 2470635B1
Authority
EP
European Patent Office
Prior art keywords
composition
compositions
ether
propylene glycol
hard surface
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.)
Active
Application number
EP10759958.1A
Other languages
German (de)
English (en)
Other versions
EP2470635A1 (fr
Inventor
Edward Matthew Cooney, Jr.
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.)
Reckitt Benckiser LLC
Original Assignee
Reckitt Benckiser LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Reckitt Benckiser LLC filed Critical Reckitt Benckiser LLC
Publication of EP2470635A1 publication Critical patent/EP2470635A1/fr
Application granted granted Critical
Publication of EP2470635B1 publication Critical patent/EP2470635B1/fr
Active 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C11D3/43—Solvents
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to improved hard surface cleaning compositions. More particularly the present invention is directed to hard surface cleaning compositions featuring low streaking, effective against greasy soils, comprising amine oxide surfactant and phenyl containing glycol ether solvents.
  • Hard surface cleaning compositions are commercially important products and enjoy a wide field of use, and are known in assisting in the removal of dirt and grime from surfaces, especially those characterized as useful for cleaning "hard surfaces”.
  • Hard surfaces include those which are frequently encountered in lavatories, for example lavatory fixtures such as toilets, shower stalls, bathtubs, bidets, sinks, etc., as well as countertops, walls, floors, etc.
  • lavatory fixtures such as toilets, shower stalls, bathtubs, bidets, sinks, etc.
  • two types of commonly encountered stains in lavatories include "hard water” stains, "soap scum” stains as well as “rust stains”.
  • Such hard surfaces, and such stains may also be found in different environments as well, including kitchens, hospitals, etc.
  • Hard water stains are mineral stains caused by the deposition of salts, such as calcium or magnesium salts which are frequently present in hard water which is commonly encountered.
  • Soap scum stains are residues of fatty acid soaps, such as soaps which are based on alkaline salts of low fatty acids. These fatty acids are known to precipitate in hard water due to the presence of metal salts therein leaving an undesirable residue upon such surfaces.
  • Still further stains typically referred to as greasy stains, are surface residues which generally comprise hydrophobic materials often with further materials which leave unsightly residues on surfaces.
  • WO2008/155518 describes an aqueous alkaline hard surface cleaning composition.
  • compositions of the present invention are particularly directed.
  • compositions of the present invention are directed to low streaking hard surface cleaning compositions which are particularly effective in the removal of stains from hard surfaces especially glassy or polished hard surfaces, e.g., reflective hard surfaces.
  • the present invention also provides methods for the production of such low streaking hard surface cleaning compositions, as well as methods for their use.
  • the hard surface cleaning compositions of the present invention necessarily comprises:
  • compositions of the present invention exhibit good cleaning properties against dirt and stains commonly found in household, commercial and residential settings, particularly in kitchen settings wherein greasy soils and stains are frequently encountered, and concurrently exhibit reduced streaking and/or reduced residues of such cleaned surfaces.
  • compositions of the invention necessarily include at least one amine oxide surfactant such as:
  • alkyl di(C 1 -C 2 ) amine oxides in which the alkyl group has 10-14, and preferably has 12 carbon atoms, which are preferably saturated.
  • lauryl dimethyl amine oxide which in preferred embodiments is present to the exclusion of other amine oxides.
  • the amine oxide surfactant(s) present comprise 0.01 - 1.5%wt., preferably 0.1 - 0.7%wt and especially preferably 0.3 - 0.55%wt of the compositions of the present invention..
  • inventive compositions are preferably essentially free of anionic and cationic surfactants, and in especially preferred embodiments the inventive compositions are essentially free of further anionic, cationic, nonionic, amphoteric and zwitterionic surfactants other than the amine oxide surfactants identified above.
  • amine oxide surfactants are the sole species of surfactants present in the compositions.
  • compositions of the invention comprises at least one C 1 -C 3 monohydric alcohol being exclusively isopropanol which has been found to be particularly effective.
  • the C 1 -C 3 monohydric alcohols comprise 0.5 - 6%wt., preferably 1.5 - 5%wt and especially preferably 2 - 4%wt of the inventive compositions.
  • Isopropanol is the sole C 1 -C 3 monohydric alcohol present.
  • compositions of the invention additionally comprise one or more phenyl containing glycol ether solvents including those which may be represented by the following general structural representation (I): wherein R is a C 1 -C 6 alkyl group which contains at least one -OH moiety, and preferably R is selected from: CH 2 OH, CH 2 CH 2 OH, CH(OH)CH 3 , CH(OH)CH 2 OH, CH 2 CH 2 CH 2 OH, CH 2 CH(OH)CH 3 , CH(OH)CH 2 CH 3 , CH(OH)CH 2 CH 2 OH, CH(OH)CH(OH)CH 3 , and CH(OH)CH(OH)CH 2 OH, and the phenyl ring may optionally substituted with one or more further moieties such as C 1 -C 3 alkyl groups but is preferably unsubstituted.
  • R is a C 1 -C 6 alkyl group which contains at least one -OH moiety, and preferably R is selected from: CH 2 OH, CH 2
  • a specific useful phenyl containing glycol ether solvent is commercially supplied as DOWANOL PPH, described to be a propylene glycol phenyl ether which is described by it supplier as being represented by the following structural representation (II): and further, indicated is that the major isomer is as indicated, which suggests that other alkyl isomers are also present.
  • the sole phenyl containing glycol ether solvent present in the compositions is propylene glycol phenyl ether which has been found to be unusually effective.
  • the phenyl containing glycol ether solvents comprise 0.05 - 0.85%wt., preferably 0.1 - 0.4 %wt and especially preferably 0.18 - 0.38%wt of the inventive compositions.
  • compositions of the invention further additionally comprise a non-phenyl moiety containing glycol ether organic solvents.
  • the non-phenyl moiety containing glycol ether organic solvent comprises 0 - 5%wt., preferably 0.1 - 2 %wt., and preferably 0.95 -2.2%wt, and particularly preferably 1 - 1.75%wt. of the inventive compositions.
  • Propylene glycol n-butyl ether is the sole non-phenyl moiety containing, viz., aliphatic, glycol ether organic solvent present.
  • compositions concurrently comprise each of: 2 - 4%wt. isopropanol, 0.19 - 0.4%wt., but preferably 0.19 - 0.3%wt. propylene glycol phenyl ether and I - 1.5%wt. propylene glycol n-butyl ether which are present, to the exclusion of any further organic solvents in the compositions.
  • the inventor has unexpectedly and surprisingly discovered that highly effective, largely aqueous cleaning compositions suited for the cleaning of grease laden hard surfaces, while at the same time being essentially low residue, low streaking or "streak free" may now be produced particularly in compositions which include amine oxide based surfactants to the exclusion of further cationic and anionic surfactants, concurrently with the preferred organic solvent systems described herein.
  • compositions also necessarily include one or more alkanolamines, which may provide alkalinity to compositions, as well as simultaneously providing excellent removal of hydrophobic soils which may be encountered, e.g., greases and oils.
  • alkanolamines are not considered to be organic solvents.
  • Exemplary useful alkanolamines include monoalkanolamines, dialkanolamines, trialkanolamines, and alkylalkanolamines such as alkyl-dialkanolamines, and dialkylmonoalkanolamines.
  • the alkanol and alkyl groups are generally short to medium chain length, that is, from 1 to 7 carbons in length.
  • the alkanolamine constituent may be a single alkanolamine, or may be a plurality of alkanolamines as well. Particularly preferred as the alkanolamine constituent is monoethanolamine which has found to be effective both as an alkalinity source and as a cleaning component.
  • the alkalinity constituent of the invention consists solely of a single alkanolamine, preferably selected from monoalkanolamines, dialkanolamines, trialkanolamines of 1 to 7 carbons in length, preferably is a single monoalkanolamine selected from linear monoethanolamine, monopropanolamine or monobutanolamine, and especially preferably is monoethanolamine, which is advantageously present to the exclusion of other alkanolamines.
  • the one or more alkanolamines comprise 0.1 - 5%wt. , preferably 0.5 - 2.5%wt and especially preferably 0.5 - 0.8%wt of the inventive compositions.
  • the compositions include 0 to 0.0005%wt of an antifoaming agent, typically silicone antifoaming agents comprising silicone and siloxane polymers often provided as emulsions in water.
  • an antifoaming agent typically silicone antifoaming agents comprising silicone and siloxane polymers often provided as emulsions in water.
  • a particularly suitable antifoam agent is a polydimethylsiloxane composition. It has been observed that the inclusion of a minor amount of antifoam agent is advantageously used the compositions described herein to reduce foaming tendencies of the compositions, such that a brief visible foam is present and seen when the compositions are wiped on a surface but quickly breaks and dissipates and thus does not leave undesired residues on the treated surface.
  • an antifoaming constituent may be excluded from the compositions taught herein, advantageously they are present in amounts of from 0.0001 - 0.002%wt., based on the weight of the silicone and/or siloxane compounds of the compositions of which they form a part. Surprisingly even such small amounts of this constituent were found to be effective.
  • compositions include a hydrotrope which primarily fulfills the function of improving the solubility of any fragrance constituent present in the largely aqueous compositions taught herein.
  • a hydrotrope which primarily fulfills the function of improving the solubility of any fragrance constituent present in the largely aqueous compositions taught herein.
  • Such a constituent may be omitted however if desired but is advantageously present.
  • Exemplary hydtropes include, inter alia, benzene sulfonates, naphthalene sulfonates, C 1 -C 11 alkyl benzene sulfonates, naphthalene sulfonates, C 5 -C 11 alkyl sulfonates, C 6 -C 11 alkyl sulfates, alkyl diphenyloxide disulfonates, and phosphate ester hydrotropes.
  • the hydrotropic compounds of the invention are often provided in a salt form with a suitable counterion, such as one or more alkali, or alkali earth metals, such as sodium or potassium, especially sodium.
  • alkyl benzene sulfonates include, for example, isopropylbenzene sulfonates, xylene sulfonates, toluene sulfonates, cumene sulfonates, as well as mixtures thereof.
  • Exemplary C 5 -C 11 alkyl sulfonates include hexyl sulfonates, octyl sulfonates, and hexyl/octyl sulfonates, and mixtures thereof.
  • Particularly useful hydrotrope compounds include benzene sulfonates, o-toluene sulfonates, m-toluene sulfonates, and p-toluene sulfonates; 2,3-xylene sulfonates, 2,4-xylene sulfonates, and 4,6-xylene sulfonates; cumene sulfonates, wherein such exemplary hydrotropes are generally in a salt form thereof, including sodium and potassium salt forms.
  • compositions taught herein are present in amounts of from about 0.001 - 2%wt., preferably 0.01-0.5 %wt and especially preferably 0.1 - 0.3%wt of the present inventive compositions.
  • inventive compositions may comprise, up to a cumulative total of 10%wt, but preferably a cumulative total of 5%wt. of one or more conventional additives selected coloring agents, fragrances and fragrance solubilizers, viscosity modifying agents including one or more thickeners, pH adjusting agents and pH buffers including organic and inorganic salts, optical brighteners, abrasives, and preservatives, as well as other optional constituents known to the art.
  • any such conventional additive constituent which undesirably diminishes the preferred low streaking characteristics of the invention are expressly omitted from the compositions.
  • Preservatives may also be added in minor amounts in the compositions according to the invention, e.g., including those which are presently commercially available under the trademarks Kathon® CG/ICP (Rohm & Haas, Philadelphia Pa.), Suttocide® A (Sutton Labs, Chatham N.J.) as well as Midtect® TFP (Tri-K Co., Emerson, N.J.).
  • Such may be included in minor amounts, e.g., 0.0001 to 0.5% by weight of the total concentrate composition, more generally an amount of 0.1% by weight and less, and preferably present in amounts of 0.05% by weight and less.
  • the concentrate compositions of the invention optionally but in certain cases desirably include a fragrance constituent.
  • Fragrance compositions as received from a supplier may be provided as an aqueous or organically solvated composition, and may include as a hydrotrope or emulsifier a surface-active agent, typically a surfactant, in minor amount, generally not in excess of 1.5%wt.
  • a fragrance constituent may be present in any effective amount, but are typically comprises not more than 2%wt, preferably not more than 1%wt. of the composition.
  • Thickeners such as clays, cross-linking acrylic polymers, e.g. CARBOPOL, gums, celluloses including modified celluloses, and the like are desirably excluded as such are expected to reduce the preferred low streaking characteristics of preferred embodiments of the invention.
  • abrasive materials such as: oxides, e.g., calcined aluminum oxides and the like, carbonates, e.g., calcium carbonate and the like, quartzes, siliceous chalk, diatomaceous earth, colloidal silicon dioxide, alkali metasilicates, e.g., sodium metasilicate and the like, perlite, pumice, feldspar, calcium phosphate, organic abrasive materials based on comminuted or particulate polymers especially one or more of polyolefins, polyethylenes, polypropylenes, polyesters, polystyrenes, acetonitrile-butadiene-styrene resins, melamines, polycarbonates, phenolic resins, epoxies and polyurethanes, natural materials such as, for example, rice hulls, corn cobs, and the like, or talc and mixtures thereof, and the like are desirably excluded as such are expected to
  • compositions of the invention expressly exclude organic acids, e.g., citric, malic, succinic, lactic, glycolic, fumaric, tartaric, and formic, etc.
  • organic acids e.g., citric, malic, succinic, lactic, glycolic, fumaric, tartaric, and formic, etc.
  • compositions of the invention may include one or more pH adjusting agents, or compounds which may be use to adjust the pH of the compositions, or to buffer the pH of the compositions of which they form a part. However such is frequently unnecessary due to the inclusion of the alkanolamine constituent, which imparts alkalinity to the compositions.
  • compositions of the invention expressly exclude inorganic acids, e.g., sulfuric acid, phosphoric acid, potassium dihydrogenphosphate, sodium dihydrogenphosphate, sodium sulfite, potassium sulfite, sodium pyrosulfite (sodium metabisulfite), potassium pyrosulfite (potassium metabisulfite), acid sodium hexametaphosphate, acid potassium hexametaphosphate, acid sodium pyrophosphate, acid potassium pyrophosphate, , hydrochloric acid, and sulfamic acid.
  • inorganic acids e.g., sulfuric acid, phosphoric acid, potassium dihydrogenphosphate, sodium dihydrogenphosphate, sodium sulfite, potassium sulfite, sodium pyrosulfite (sodium metabisulfite), potassium pyrosulfite (potassium metabisulfite), acid sodium hexametaphosphate, acid potassium hexametaphosphate,
  • compositions are highly aqueous and comprise at least 90%wt. water, which is preferably distilled, demineralized but especially preferably is deionized water.
  • compositions are readily pourable and pumpable, and are liquids at room temperature, exhibiting a viscosity in the range of from 1 cP to 50 cP at such environmental conditions.
  • compositions typically exhibit a pH in the range of 9.5 - 11.5, preferably in the range of 10.5 - 11.35.
  • compositions are easily produced by any of a number of known art techniques.
  • a part of the water is supplied to a suitable mixing vessel further provided with a stirrer or agitator, and while stirring, the remaining constituents are added to the mixing vessel, including any final amount of water needed to provide to 100%wt. of the inventive composition.
  • composition provided according to the invention can be desirably provided as a consumer product in a manually openable and resealable storage container, which may be either rigid or may be a deformable "squeeze bottle” type dispenser.
  • a manually openable and resealable storage container which may be either rigid or may be a deformable "squeeze bottle” type dispenser.
  • the composition is advantageously provided in a bottle, flask or other reservoir and dispensed via a nozzle or a pump, e.g., a manually operable pump or a manually operable trigger spray to a hard surface requiring treatment.
  • the inventive compositions may also be provided to a pressurizable container, e.g., an aerosol container with a suitable amount, typically up to 10%wt.
  • an aerosol propellant e.g., a hydrocarbon, of from 1 to 10 carbon atoms, such as n-propane, n-butane, isobutane, n-pentane, isopentane, and mixtures thereof or a non-hydrocarbon gas, e.g., CO 2 , N 2 , etc. or for that matter, even pressurized air.
  • a hydrocarbon of from 1 to 10 carbon atoms, such as n-propane, n-butane, isobutane, n-pentane, isopentane, and mixtures thereof or a non-hydrocarbon gas, e.g., CO 2 , N 2 , etc. or for that matter, even pressurized air.
  • the composition may be applied directly from a product container as a liquid, or may be applied as a wipe article preimpregnated with a quantity of the said composition.
  • Cleaning of a hard surface may be effectuated by applying a cleaning effective amount of a composition according to any preceding claim, and optionally thereafter wiping the treated hard surface to remove at least a part of the composition from the hard surface.
  • hard surfaces include surfaces composed of refractory materials such as: glazed and unglazed tile, brick, porcelain, ceramics as well as stone including marble, granite, and other stones surfaces; glass; metals; plastics e.g. polyester, vinyl, fiberglass and other hard surfaces known to the industry.
  • Hard surfaces which are to be particularly denoted are surfaces normally encountered in a lavatory, e.g., lavatory fixtures, shower stalls, bathtubs and bathing appliances (racks, curtains, shower doors, shower bars) toilets, bidets, wall and flooring surfaces as well as those associated with kitchen environments and other environments associated with food preparation, including cabinets and countertop surfaces as well as walls and floor surfaces especially those which include refractory materials, plastics, Formica®, Corian® and stone.
  • the inventive compositions are particularly effective in the cleaning treatment of polished or reflective surfaces, e.g, glazed enameled surfaces, glazed ceramic surfaces, glass, mirror surfaces, metals and polished metal surfaces and the like.
  • Illustrative example compositions which were produced include those set forth below.
  • the illustrative example compositions demonstrate particularly preferred embodiment of the invention as well as preferred weight percentages as well as preferred relative weight percentages/weight ratios with regard to the respective individual constituents present within the composition.
  • inventive hard surface treatment compositions are described in the following Table 1; the constituents indicated on Table 1 used to produce the formulations were used on an "as supplied" basis; the identity of these constituents are disclosed in more detail on Table 2.
  • the hard surface treatment compositions were produced by mixing the constituents into water as outlined in Table 1 in a beaker at room temperature which was stirred with a conventional magnetic stirring rod or paddle mixer; stirring continued until the formulation was homogenous in appearance. It is to be noted that the constituents might be added in any order, but it is preferred that a first premixture is made of any fragrance constituent with one or more surfactants and/or hydrotrope in an aliquot of water used in the inventive hard surface treatment compositions.
  • the order of addition is not critical, but good results are obtained where the surfactants (which may be also the premixture of the fragrance and surfactants) are produced prior to the addition of the remaining constituents to the water.
  • the amounts of the named constituents are indicated in %w/w based on a total weight of the hard surface treatment composition of which they form a part. The total amount of water present in each composition was based on the amount of water provided via one or more of the named constituents.
  • Table 1 also illustrates a series of "comparative examples" which were made in a similar manner, which are identified by a "C" preceding a digit.
  • Table 1 C1 1 2 3 4 5 6 anionic surfactant 1.67 -- -- -- -- -- Ammonyx LO (30%) - 1.67 1.67 1.67 1.67 1.67 monoethanolamine 0.71 0.71 0.71 0.71 0.71 0.71 (85%)
  • Dowanol PPH (93%) 0.2 0.2 0.4 0.3 0.4 0.3 0.3
  • Ammonyx LO (30%) lauryl dimethyl amine oxides (30%wt. actives) ex. Stepan Co. monoethanolamine (85%) monoethanalamine (85%wt. actives) ex. Huntsman Corp. Dowanol PPH (93%) propylene glycol phenyl ether (93 %wt. actives) ex. Dow Chem. Co. Dowanol PnB propylene glycol n-butyl ether (100%wt. actives) ex. Dow Chem. Co. Isopropanol isopropanol (99% wt. actives) propylene glycol propylene glycol (100%wt.
  • compositions were tested and evaluated according to one or more of the following test protocols.
  • compositions according to present invention as well as comparative examples based on commercial products was evaluated in accordance with the following test protocol which was used to evaluate cleaning efficacy of baked on, tough greasy soils on a hard surfaces.
  • a "baked greasy test soil” was prepared from “Part I” and “Part II” soils which were prepared as follows.
  • Part I soil was prepared by mixing together the ingredients indicated on the following table Part I soil %w/w Peanut oil 26.2 Corn oil 14.5 Cherry pie filling 14.5 Ground beef 14.5 Ground pork 14.5 Accent® (monosodium glutamate flavor aid) 0.60 Table salt 0.60 Deionized water 14.6 and thereafter baking the mixture in a glass baking dish at 400°F (205°C) for 2 hours.
  • the Part I soil was allowed to cool to 100°C or less.
  • the Part I may be divided into aliquots for later use and refrigerated in glass jars. If a refrigerated aliquot is later used, it is first heated in a hot water bath to 100°C and stirred or shaken prior to mixture with an amount of the Part II soil.
  • the Part II soil was "Kitchen Bouquet®", a commercially available bottled food product used to flavor and color gravy; it is believed to be primarily burnt sugar caramel, which is used "as supplied” from the manufacturer.
  • the baked greasy test soil used in the evaluation is mixed immediately prior to soiling test tiles by combining 83.3%wt. of the Part I soil at a temperature of 100°C with 16.7%wt. of the Part II by blending in a laboratory beaker for a minimum of 5 minutes using a hand held homogenizer.
  • test substrates white porcelain enameled steel tiles (4 inches by 4 inches) in size were used.
  • the enameled tiles are all first cleaned with mild hand dishwashing detergent, wiped with ethanol and placed in vertical racks and allowed to dry and cool to room temperature, approx. 68°F (20°C).
  • the baked greasy test soil was heated to 100°C in a water bath, and kept homogenized during application to test tiles to avoid settling of the test soil. Prior to application of the test soil, each tile was weighed. The test soil was thereafter applied to the dry test tiles by depositing 0.75 grams (+/- 0.10 grams) on the porcelain surface of each test tile using a small kitchen basting brush which was used to uniformly distribute said soil. After application, the test tile was reweighed to assure that at least 0.75 grams were deposited on the tile. If needed, a few additional drops of the baked greasy soil was applied to the tile, and applied by brushing and the tile reweighed to ensure that at least 0.75 grams of the baked greasy soil were deposited on the tile.
  • Standard sized cellulose test sponges approximately 10 cm by 7.6 cm sponges were subjected to three rinse and spin dry cycles in a domestic laundry washing machine in order to ensure that all soils, detergents or other contaminants were flushed from the sponges. After the third spin cycle, the sponge were removed from said machine and placed in a tightly sealed plastic container to maintain cleanliness as well as their relative dampness prior to their use in a cleaning evaluation.
  • a soiled test tile prepared as indicated above was placed in a SHEEN wet abrasion scrub tester (Reference: 903PG) and secured.
  • the dampened sponges were overwrapped with a nonporous polymer film in order to enclose the sponges and provide a liquid barrier between the sponge and a composition to be tested.
  • a 50 ml amount of a composition was loaded onto a uniformly sized sheet of dry wipe, e.g., a dry paper towel, which was then wrapped to enrobe a polymer film wrapped sponge, and then inserted into the holder of the SHEEN tester.
  • a 200 gram weight was added to each of the sponge holders in order to ensure compression of the sponge and good surface scrubbing of the soiled test tile with the wetted paper towel
  • the SHEEN tested was then actuated and controlled to provide 3 cleaning cycles (6 linear strokes over the surface) over the test soil on a test substrate, and thereafter the test substrate was removed, rinsed with approximately equal amounts of tap water, and dried with compressed air from an airbrush compressor. This test was repeated several times for each composition in order to provide at least 3 replicates for each tested composition.
  • the cleaning efficacy of the tested compositions was evaluated utilizing a high resolution digital imaging system which evaluated the light reflectance characteristics of the each treated test substrate.
  • This system utilized a photographic copy stand mounted within a light box housing which provided diffuse, reflected light supplied by two 15 watt, 18 inch type T8 fluorescent bulbs rated to have a color output of 4100K which approximated "natural sunlight" as noted by the manufacturer.
  • the two fluorescent bulbs were positioned parallel to one another and placed parallel and beyond two opposite sides of the test substrate (test tile) and in a common horizontal plane parallel to the upper surface of the test substrate being evaluated, and between the upper surface of the tile and the front element of the lens of a CCD camera.
  • the CCD camera was a "QImaging Retiga series" CCD camera, with a Schneider-Kreuznach Cinegon Compact Series lens, f1.9/10mm, 1 inch format (Schneider-Kreuznach model #21-1001978) which CCD camera was mounted on the copy stand with the lens directed downwardly towards the board of the copy stand on which a treated test substrate was placed directly beneath the lens.
  • the light box housing enclosed the photographic copy stand, the two 18 inch fluorescent bulbs and a closeable door permitted for the insertion, placement and withdrawal of a treated test substrate which door was closed during exposure of the CCD camera to a treated test substrate. In such a manner, extraneous light and variability of the light source during the evaluation of a series of tested substrates was minimized, also minimizing exposure and reading errors by the CCD camera.
  • the CCD camera was attached to a desktop computer via a Firewire IEEE 1394 interface and exposure data from the CCD camera was read by a computer program, "Media Cybernetics Image Pro Plus v. 6.0", which was used to evaluate the exposures obtained by the CCD camera, which were subsequently analyzed in accordance with the following.
  • a 12 inch by 12 inch glass mirror tile was cleaned and thoroughly rinsed with water to ensure the removal of any surface deposits, and subsequently the surface of the mirror was wiped with alcohol applied with a disposable lint free laboratory wipe (Kimwipe®, ex. Kimberly- Clark, Inc.)
  • drying rate the performance of a tested composition was evaluated according to the following scale: "10" indicated total product drying within about 3 seconds; “9” indicated total product drying within about 6 seconds; “8” indicated total product drying within about 9 seconds; “7” indicated total product drying within about 12 seconds; “6” indicated total product drying within about 15 seconds; “5" indicated total product drying within about 18 seconds; “4" indicated total product drying within about 21 seconds; “3” indicated total product drying within about 24 seconds; “2” indicated total product drying within about 3 seconds and a rate of "1" indicated total product drying within about 30 seconds or more.
  • compositions of the invention particularly E1, E3, E5 and E6 concurrently provided both excellent cleaning of greasy surfaces and at the same time exhibited essentially streak free and low residue cleaning benefit on the tested substrates.
  • the compositions of the invention provided superior cleaning performance than the commercially available FLASH product, which exhibited a high degree of streaking but satisfactory cleaning of greasy surfaces, and low streaking and fast drying characteristics comparable to a commercially available glass cleaning product, VIGOR (ex. Eau Ecarlate S.A.S., France).

Landscapes

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

Claims (6)

  1. Composition de nettoyage d'une surface dure laissant peu de traces, comprenant :
    0,01-1,5% en poids d'un ou plusieurs agents tensioactifs à base d'oxyde d'amine ;
    0,5-6% en poids d'un solvant à base d'alcool monohydrique en C1-C3 ;
    0,05-0,85% en poids d'un solvant à base de glycol éther phénylé ;
    0 à 5% en poids d'un solvant organique à base de glycol éther non phénylé ;
    0,1-5% en poids d'une alcanolamine ;
    0 à 0,005% en poids, préférablement 0,0001-0,002% en poids d'un constituant antimousse à base de silicone ;
    0 à 0,5% en poids d'un hydrotrope ;
    au moins 90% en poids d'eau ;
    et éventuellement, un ou plusieurs autres additifs classiques selon une quantité cumulée n'excédant pas 10% en poids du total de la composition dont ils font partie, où les compositions comprennent comme seuls solvants organiques présents :
    de l'isopropanol, du propylène glycol phényléther et du propylène glycol n-butyléther,
    caractérisée en ce que la composition exclut d'autres agents tensioactifs cationiques et anioniques et comprend un liquide aisément pompable et versable présentant une viscosité allant de 1 à 50 cP dans de telles conditions environnementales.
  2. Composition selon la revendication 1, comprenant 0,1-0,7% en poids d'un ou plusieurs agents tensioactifs à base d'oxyde d'amine.
  3. Composition selon la revendication 1, comprenant chacun parmi : 2-4% d'isopropanol, 0,19-0,4% en poids, mais préférablement 0,19-0,3% en poids, de propylène glycol phényléther et environ 1-1,5% en poids de propylène glycol n-butyléther.
  4. Composition selon la revendication 1, comprenant chacun parmi : 0,185-0,3% en poids, mais préférablement pas plus de 0,3% en poids, de propylène glycol phényléther ; une masse totale combinée de 1-2% en poids, préférablement de 1,2-1,8% en poids, de propylène glycol n-butyléther et de dipropylène glycol monobutyléther, où le rapport pondéral du premier au dernier est de 0,1-0,3:1, préférablement est de 0,15-0,2:1 du premier au dernier sur une base pondérale ; et 2-4% en poids, mais préférablement 3-4% en poids, d'isopropanol.
  5. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le pH de la composition se trouve dans la plage de 9,5-11,5.
  6. Procédé de nettoyage d'une surface dure, comprenant l'étape consistant à :
    appliquer une quantité efficace nettoyante d'une composition selon l'une quelconque des revendications précédentes, puis éventuellement ensuite essuyer la surface dure traitée pour éliminer au moins une partie de la composition à partir de la surface dure.
EP10759958.1A 2009-10-08 2010-09-14 Composition nettoyante pour surfaces dures Active EP2470635B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0917597A GB2474260A (en) 2009-10-08 2009-10-08 Hard surface cleaning composition
PCT/GB2010/051541 WO2011042714A1 (fr) 2009-10-08 2010-09-14 Composition nettoyante pour surfaces dures

Publications (2)

Publication Number Publication Date
EP2470635A1 EP2470635A1 (fr) 2012-07-04
EP2470635B1 true EP2470635B1 (fr) 2014-08-20

Family

ID=41402700

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10759958.1A Active EP2470635B1 (fr) 2009-10-08 2010-09-14 Composition nettoyante pour surfaces dures

Country Status (5)

Country Link
EP (1) EP2470635B1 (fr)
AU (1) AU2010304850B2 (fr)
GB (1) GB2474260A (fr)
RU (1) RU2560169C2 (fr)
WO (1) WO2011042714A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105316117A (zh) * 2015-12-02 2016-02-10 苏州龙腾万里化工科技有限公司 一种防雾玻璃清洁剂
CN105296171A (zh) * 2015-12-02 2016-02-03 苏州龙腾万里化工科技有限公司 一种低泡玻璃清洁剂
US11441103B2 (en) 2017-01-16 2022-09-13 United Laboratories International, Llc Solvent composition and process for cleaning contaminated industrial equipment
CA3139842A1 (fr) * 2019-05-10 2020-11-19 The Procter & Gamble Company Compositions de nettoyage de surfaces dures comportant des phenols alcoxyles et des parfums et tampons de nettoyage et procedes pour l'utilisation desdites compositions
US11859158B2 (en) * 2019-12-03 2024-01-02 The Procter & Gamble Company Hard surface cleaning composition and method of improving surface shine using the same
RU2762633C1 (ru) * 2021-04-29 2021-12-21 Общество с ограниченной ответственностью "ХИМИЖ" Омывающая незамерзающая жидкость

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0630965A1 (fr) * 1993-06-23 1994-12-28 The Procter & Gamble Company Compositions détergentes liquides concentrées pour surfaces dures contenant des copolymères d'acide maleique-oléfine
JP4257201B2 (ja) * 2001-07-20 2009-04-22 ザ プロクター アンド ギャンブル カンパニー 溶媒系を含む硬質面用洗浄性組成物
US20090099057A1 (en) * 2006-03-03 2009-04-16 Reckitt Benckiser, Inc. Hard Surface Cleaning Composition
EP1991653A1 (fr) * 2006-03-03 2008-11-19 Reckitt Benckiser Inc. Préparation nettoyante pour surface dure
GB0711992D0 (en) * 2007-06-21 2007-08-01 Reckitt Benckiser Inc Alkaline hard surface cleaning composition

Also Published As

Publication number Publication date
EP2470635A1 (fr) 2012-07-04
GB0917597D0 (en) 2009-11-25
RU2560169C2 (ru) 2015-08-20
GB2474260A (en) 2011-04-13
WO2011042714A1 (fr) 2011-04-14
RU2012118607A (ru) 2013-11-20
AU2010304850B2 (en) 2013-02-28
AU2010304850A1 (en) 2012-04-19

Similar Documents

Publication Publication Date Title
US6559111B2 (en) Acidic hard surface cleaning and disinfecting compositions which include silicone quarternary ammonium salts
US7368417B2 (en) Hard surface cleaning compositions comprising a lauryl hydroxysultaine
EP2406364B1 (fr) Composition de nettoyage
US6376448B1 (en) Alkaline hard surface cleaning and disinfecting compositions including silicone quarternary ammonium salts
JP6813578B2 (ja) 洗浄製品
US20100234269A1 (en) Environmentally Acceptable Hard Surface Treatment Compositions
EP2470635B1 (fr) Composition nettoyante pour surfaces dures
JP2008516012A (ja) 軽質液体洗剤組成物
JP2008533253A (ja) アセタールを有機溶剤として含有する洗剤および清浄剤
US20110277786A1 (en) Highly acidic hard surface treatment compositions featuring good greasy soil and soap scum removal
JP2004059806A (ja) 硬表面用洗浄剤組成物
US6232283B1 (en) Liquid detergent composition
EP2029717B1 (fr) Compositions moussantes de nettoyage de surfaces dures
DK160152B (da) Flydende alsidigt rensemiddel
JP6679153B2 (ja) 硬質表面用液体洗浄剤組成物
US11104865B2 (en) Dishwash composition comprising rinse-activatable antifoam
JP2018115321A (ja) 洗浄製品
JP4698009B2 (ja) 浴室用硬表面洗浄剤組成物
JP2022038114A (ja) 硬質表面用洗浄剤組成物
JPH09235592A (ja) 液体洗浄剤組成物
JP2020056039A (ja) 硬質表面の洗浄方法
JP2022013160A (ja) 硬質表面の清拭洗浄用組成物
US20200095521A1 (en) Shelf Stable Formulations for Home, Institution and Industrial Uses
AU2004200098A1 (en) Acidic hard surface cleaning and disinfecting compositions

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: 20120323

AK Designated contracting states

Kind code of ref document: A1

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

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20130618

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140526

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

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: 683496

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140915

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602010018415

Country of ref document: DE

Effective date: 20141002

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 683496

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140820

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20140820

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: NO

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

Effective date: 20141120

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: 20140820

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: 20141121

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: 20140820

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: 20141120

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: 20141222

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: 20140820

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: 20140820

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

Ref country code: HR

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

Effective date: 20140820

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: 20140820

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: 20141220

Ref country code: AT

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: 20140820

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: 20140820

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

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: 20140820

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: 20140820

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: 20140820

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: 20140820

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: 20140820

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602010018415

Country of ref document: DE

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

Effective date: 20140820

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: 20140820

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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: 20140930

26N No opposition filed

Effective date: 20150521

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

Ref country code: LI

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

Effective date: 20140930

Ref country code: CH

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

Effective date: 20140930

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

Ref country code: IE

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

Effective date: 20140914

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: 20140820

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

Ref country code: SM

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: 20140820

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

Ref country code: MT

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

Effective date: 20140820

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: 20140820

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; INVALID AB INITIO

Effective date: 20100914

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: 20140820

Ref country code: LU

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

Effective date: 20140914

Ref country code: BE

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: 20140820

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

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

Ref country code: MK

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: 20140820

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

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

Ref country code: AL

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: 20140820

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

Ref country code: GB

Payment date: 20180927

Year of fee payment: 16

Ref country code: IT

Payment date: 20180919

Year of fee payment: 9

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602010018415

Country of ref document: DE

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

Ref country code: DE

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

Effective date: 20200401

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

Ref country code: IT

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

Effective date: 20190914

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

Effective date: 20190914

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: 20190914

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230513

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

Ref country code: FR

Payment date: 20230710

Year of fee payment: 14