EP2519623B1 - Phosphatsubstitute für membrankompatible reinigungs- und/oder waschmittelzusammensetzungen - Google Patents

Phosphatsubstitute für membrankompatible reinigungs- und/oder waschmittelzusammensetzungen Download PDF

Info

Publication number
EP2519623B1
EP2519623B1 EP09852770.8A EP09852770A EP2519623B1 EP 2519623 B1 EP2519623 B1 EP 2519623B1 EP 09852770 A EP09852770 A EP 09852770A EP 2519623 B1 EP2519623 B1 EP 2519623B1
Authority
EP
European Patent Office
Prior art keywords
acid
composition
copolymer
composition according
membrane
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
EP09852770.8A
Other languages
English (en)
French (fr)
Other versions
EP2519623A1 (de
EP2519623B2 (de
EP2519623A4 (de
Inventor
Amila Bilic
Ralf-Erbo Knop
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.)
Ecolab Inc
Original Assignee
Ecolab Inc
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=44226206&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2519623(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Ecolab Inc filed Critical Ecolab Inc
Publication of EP2519623A1 publication Critical patent/EP2519623A1/de
Publication of EP2519623A4 publication Critical patent/EP2519623A4/de
Publication of EP2519623B1 publication Critical patent/EP2519623B1/de
Application granted granted Critical
Publication of EP2519623B2 publication Critical patent/EP2519623B2/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to a cleaning or detergent composition as defined in claim 1 comprising 5 to 30 wt.-% of a phosphate substitute, said phosphate substitute comprising a water-soluble copolymer and a multidentate chelating agent, the composition being free from any phosphates, silicates and cellulose-based compounds.
  • Phosphates bind calcium and magnesium ions and are able to disperse insoluble salts of these ions, e.g. calcium carbonate causing water hardness and leading to spotting on hard surfaces and graying in textiles. Phosphates furthermore can act as alkalinity source for the cleaning or detergent composition, while at the same time being able to buffer the wash liquor above pH 9 in combination with further additives.
  • phosphate substitutes should nevertheless fulfill the different functions of phosphate in cleaning and/or detergent compositions mentioned above, namely (1) complexing of magnesium and calcium ions, (2) dispersing capacity for insoluble salts of these ions, for example calcium carbonate, (3) providing alkalinity, and (4) buffering capacity.
  • zeolites being alumino silicates
  • zeolites have a high binding constant for magnesium and calcium ions and are able to sequester free magnesium and calcium cations.
  • zeolites are insoluble in water and their incorporation in cleaning and detergent compositions can lead to undesirable residues being deposited on the surfaces/fabrics to be cleaned.
  • cleaning and detergent compositions comprising high levels of zeolite builders form undesirable cloudy wash liquors upon contact with water. For this reason zeolites are commonly used in combination with further additives in order to improve their performance and activity.
  • phosphate substitute builders based on zeolites or mixtures of zeolites with further compounds are suitable for various household applications, they are not for institutional and industrial processes, as in these processes, the wastewater generated in the automatic cleaning/washing process is usually cleaned and purified using a membrane filtration step.
  • the purified water obtained from this membrane filtration step can afterwards be reused in further washing cycles, thus reducing the need of fresh water required to be added in the washing cycle, saving resources and reducing costs.
  • WO 2005/118760 and WO 2008/110205 A1 both describe a membrane-friendly pasty soap composition comprising a combination of an acrylic/maleic copolymer and the trisodium salt of nitrilotriacetic acid (NTA) as a builder system.
  • NTA nitrilotriacetic acid
  • WO 2007/101470 A1 describes a liquid membrane-compatible detergent composition comprising a mixture of an acrylic-maleic copolymer and the sodium salt of methyl glycine diacetic acid (MGDA) in a ratio of 1:1. While the specific detergents and cleaning compositions described in this application show a good washing performance even in hard water, it is explicitly stated in WO 2007/101470 A1 that fatty acid soaps must not be present in such compositions as they tend to form lime soaps in the presence of hard water which block the membranes of the membrane filtration unit.
  • MGDA methyl glycine diacetic acid
  • a cleaning or detergent composition comprising one or more surfactant components as defined in claim 1, one or more alkalinity sources, water, and 5 to 30 wt.-%, based on the whole composition, of a phosphate substitute, comprising:
  • the substitute exhibits an improved membrane compatibility in comparison to the phosphate substitutes known in the art, in particular with respect to membrane capacity and membrane cleaning results, even in the presence of fatty acids or the soaps derived therefrom.
  • Detergent compositions comprising this substitute showed good cleaning properties as well.
  • the amount of 5 to 30 wt.-% relates to the amount of the complete phosphate substitute mixture, i.e. to the amount of the mixture of the water-soluble copolymer and the chelating agent.
  • the cleaning/detergent composition comprises 15 wt.-% of a phosphate substitute comprising the copolymer and the chelating agent in a ratio of 2:1, then the cleaning/detergent composition comprises 10 wt.-% of the copolymer and 5 wt.-% of the chelating agent, based on the whole composition.
  • the phosphate substitute comprises a water-soluble copolymer.
  • a copolymer is regarded as being water-soluble if at least 100 g, more preferably at least 200 g of the polymer can be completely dissolved in one liter (1 L) of water at a temperature of 23°C.
  • a multidentate chelating agent is a compound capable of donating two or more pairs of electrons from at least two different atoms of different functional groups (complexing groups) in a complexation reaction to form coordinate bonds.
  • the multidentate chelating agent preferably comprises 3 to 6 complexing groups per molecule, which means that it preferably donates at least 3 to 6 pairs of electrons in a complexation reaction to form coordinate bonds.
  • These multidentate chelating agents form water-soluble complexes with Ca 2+ and/or Mg 2+ magnesium ions, thus preventing the formation of insoluble precipitates, which otherwise would block the membrane.
  • the calcium or magnesium complex is regarded as being water-soluble if at least 0.1 mol of this complex can be completely dissolved in one liter of water at a temperature of 23°C.
  • the composition is free from any phosphates, silicates, including zeolites, and cellulose-based compounds.
  • the cleaning/detergent compositions of the present invention are not only environmentally friendly due to the lack of phosphates, but are also suitable for the application in machine dishwashing or laundry washing processes which employ membrane filtration techniques, including reverse osmosis membranes.
  • the composition of the present invention can even be used as a cleaning agent for cleaning soiled, blocked and/or contaminated membranes, including reverse osmosis membranes.
  • the composition of the present invention comprises 6 to 27.5 wt.-%, more preferably 7.5 to 25 wt.-%, and most preferably 9 to 20 wt.-% of the phosphate substitute.
  • the amount of phosphate substitute may be adjusted to the water hardness in a particular region and to the aggregate state of the cleaning/detergent composition. If the composition of the present invention is provided in the form of a solid composition, the amount of phosphate substitute in the composition preferably is in the range of 14 to 25 wt.-%, more preferably in the range of 17 to 23 wt.-%, and even more preferably in the range of 18 to 20 wt.-%.
  • the composition of the present invention is provided in the form of a liquid laundry detergent composition
  • the composition preferably comprises between 5 and 15 wt.-% of the phosphate substitute, more preferably between 7.5 and 12 wt.-% and most preferably 8.5 to 11 wt.-%.
  • the copolymer comprised in the phosphate substitute of the present invention has a calcium carbonate dispersing capacity of at least 150 mg CaCO 3 /g copolymer, preferably of at least 175 mg CaCO 3 /g, more preferably of at least 200 mg CaCO 3 /g, even more preferably of at least 250 CaCO 3 /g and most preferably the calcium carbonate dispersing capacity of the copolymer is in the range of 280 to 320 mg CaCO 3 /g copolymer.
  • the calcium carbonate dispersing capacity referred to herein is determined according to F. Richter and E.W. Winkler, Tensides Surfactants Detergents 1987, 4, 213 - 216 , by dissolving 1 gram of the substance (copolymer) in 100 mL deionized water, neutralizing the solution, if necessary, with 1M NaOH, adding 10 mL of a 10 % Na 2 CO 3 solution, and adjusting to pH 10 by adding NaOH or HCl, as required. The solution is then titrated with a 0.25 M calcium acetate solution until the solution becomes turbid, while the pH and the temperature are kept constant during titration.
  • R, R' R" may be the same or different and are not particulary limited.
  • R, R' and R" represent hydrogen, C 1 -C 6 alkyl groups or functional groups such as carboxylates, nitriles, and the like.
  • the aliphatic unsaturated monomer units of the present invention further comprise acidic groups, preferably carboxylic groups, i.e. groups of the chemical formula -CO 2 H or their salts -CO 2 M, wherein M is an alkali metal cation.
  • the at least two different aliphatic unsaturated monomer units comprised in the water-soluble copolymer are selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride and fumaric acid, or salts thereof.
  • one aliphatic unsaturated monomer unit represents maleic acid or salts thereof and the second aliphatic unsaturated monomer unit represents acrylic acid or salts thereof.
  • the copolymer comprises 50 to 70 wt.-% acrylic acid and 50 to 10 % maleic acid.
  • the relative molecular weight of the copolymer preferably is between 2,000 and 200,000, preferably between 3,000 and 150,000, more preferably between 4,000 and 125,000, even more preferably between 12,000 and 110,000, particularly preferred between 20,000 and 100,000, even more particularly preferred between 50,000 and 90,000, and most preferably between 65,000 and 75,000, based on free acid. It should be understood that even if the preferred molecular weights are given based on the free acid, in a particularly preferred embodiment at least partly neutralized copolymers are used, i.e. polymers comprising negatively charged carboxylate groups having a positively charged alkali metal counterion, wherein these counterions preferably are sodium or potassium ions.
  • the copolymer preferably has a neutral or close to neutral pH (pH 6 to 8).
  • Suitable, but less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene
  • Other suitable polymer carboxylates or carboxylic acids are water-soluble terpolymers which contain two unsaturated acids and/or salts thereof as monomers and vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate as the third monomer.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, more preferably from (meth)acrylic acid.
  • the second acidic monomer or its salt may be a derivative of C 4 -C 8 -dicarboxylic acid, maleic acid being particularly preferred.
  • the third monomer unit in this case will be formed from a vinyl alcohol and/or preferably an esterified vinyl alcohol. Especially preferred are vinyl alcohol esters formed form a short chain carboxylic acids, like C 1 -C 4 -carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60 to 95 wt-%, particularly 70 to 90 wt.-% (meth)acrylic acid or (meth)acrylate, respectively, more particular acrylic acid or acrylate, respectively, and maleic acid or maleinate and 5 to 40 wt.-%, preferably 10 to 30 wt.-% vinyl alcohol and/or vinyl acetate.
  • the second monomer or its salt may also be a derivative of an allyl sulfonic acid substituted in the 2-position by an alkyl group, preferably a C 1 -C 4 alkyl group, or an aryl group which is preferably derived from benzene or a benzene derivative.
  • Preferred terpolymers contain 40 to 60 wt.-%, in particular 45 to 55 wt.-% (meth)acrylic acid or (meth)acrylate, more preferred acrylic acid or acrylate, 10 to 30 wt.-%, particularly 15 to 25 wt.-% methallyl sulfonic acid or methallyl sulfonate and as third monomer 15 to 40 wt.-%, preferably 20 to 40 wt.-% of a carbohydrate.
  • Said carbohydrate for example, may be a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharide being preferred. Saccharose is most preferred.
  • polymeric polycarboxylates may be produced by the method described in German patent DE 42 21 381 and German patent application DE 43 00 772 .
  • the polyacetal carboxylic acids described, for example, in U.S. Pat. Nos. 4,144,226 and 4,146,495 , which are obtained by polymerization of esters of glycolic acid, introduction of stable terminal groups and saponification to the sodium or potassium salts are also suitable, as are polymeric acids obtained by polymeriziation of acrolein and Cannizzaro disproportionation of the polymer with strong alkalis. They are essentially made of acrylic acid units and vinyl alcohol units or acrolein units.
  • the chelating agent of the present invention preferably is a so-called "polycarboxylic acid” comprising 3 to 6 carboxylic groups per molecule, either in the protonated or in the neutralized state, preferably selected from the group consisting of hydroxyethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), methylglycinediacetic acid (MGDA), glutamic acid- N,N -diacetic acid (GLDA), iminodisuccinic acid (IDSA), hydroxyiminodisuccinic acid (HIDS), ethylenediaminodisuccinic acid (EDDS), aspartic acid- N,N -diacetic acid (ASDA), salts thereof, and mixtures thereof.
  • HEDTA hydroxyethylenediaminetriacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid- N,N
  • [CaZ (m-2)- ] represents the concentration of the chelate complex
  • [Ca 2+ ] represents the concentration of free calcium ions
  • [Z m- ] represents the concentration of the chelating agent anion
  • K CaZ represents the stability constant of the chelate complex.
  • the stability constants can easily be determined by methods well known to a person skilled in the art and are also mentioned in the product information sheet provided by the manufacturers of the aforementioned chelating agents, all of which are commercially available.
  • composition of the present invention is free from any phosphates, silicates and/or cellulose-based compounds.
  • a composition is free from a compound if it contains less than 0.1 wt.-% of this compound, preferably less than 0.01 wt.-%, more preferably less than 0.001 wt.-% and preferably the composition does not contain a compound at all, i.e. the concentration of this compound is below the detection limit of the detection method typically used to detect the compound.
  • Cellulose-based compounds commonly found in detergent composition which, however, are not present in the composition of the present invention are, for example, greying inhibitors such as cellulose ethers, e.g. carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose, methylhydroxyethyl cellulose, methylhydroxypropyl cellulose, and methylcarboxymethyl cellulose.
  • greying inhibitors such as cellulose ethers, e.g. carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose, methylhydroxyethyl cellulose, methylhydroxypropyl cellulose, and methylcarboxymethyl cellulose.
  • the composition is free from ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and/or any silicon-containing compounds.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • silicon-containing compounds any silicon-containing compounds.
  • composition of the present invention foam inhibitors/antifoaming agents on a silicon basis such as, for example, polysiloxanes or silicon oil defoamers, commonly used in membrane-friendly laundry detergent compositions known in the state of the art do not have to be included in the composition of the present invention.
  • the composition of the present invention can be free from any of these compounds, while still having desirable foaming properties.
  • composition of the present invention is a membrane-friendly laundry detergent composition, additionally comprising:
  • the alkoxylated fatty alcohols of the general formula (I) preferably are ethoxylated or propoxylated alcohols obtained by reducing the carboxylic group of octanoic acid, pelargonic acid, decanoic acid, lauric acid, lauroleic acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenis acid, eleostearic acid, arachic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid and mixtures thereof.
  • the fatty acids of the general formula (II) and their salts can be exemplified by the fatty acids mentioned above.
  • the composition comprises two different alkoxylated fatty alcohols, preferably a mixture of R 1a O(C 2 H 4 O) 5-7 H and R 1b O(C 2 H 4 O) 12-16 H, wherein R 1a and R 1b may be the same or different and represent a linear or branched alkyl or alkenyl residue with 15 to 20 carbon atoms, preferably with 16 to 18 carbon atoms.
  • the composition of the present invention optionally comprises an anionic surfactant in an amount of from 0.1 to 15 wt.-%, preferably of from 1 to 5 wt.-%, and more preferably of from 1.2 to 2 wt.-%.
  • the anionic surfactant preferably is selected from from the group consisting of C 8 -C 18 alkyl sulfates, C 8 -C 18 alkyl ether sulfates, C 8 -C 18 alkyl sulfonates, C 8 -C 18 ⁇ -olefinsulfonates, sulfonated C 8 -C 18 fatty acids, C 8 -C 18 alkylbenzenesulfonates, sulfosuccinic mono- and di-C 1 -C 12 esters, C 8 -C 18 alkyl polyglycol ether carboxylates, C 8 -C 18 N-acyl taurides, C 8 -C 18 N-sarconisates, C 8
  • the composition furthermore preferably comprises one or more alkalinity sources in a total amount of 3 to 90 wt.-%, more preferably in an amount of 5 to 50 wt.-%, based on the whole composition.
  • compositions of the present invention may be provided as a liquid, a gel, an emulsion, a paste or a solid, including tablets, granules, powders, blocks. If the composition is in a solid form or, in the case of a pasty composition, has a solid phase, the solid phase is formed from the alkalinity source (and the phosphate substitute). Accordingly, a solid or paste-like composition comprises a higher amount of alkalinity sources than a liquid or a gel composition.
  • a powdered laundry detergent composition according to the present invention preferably comprises 20 to 60 wt.-% of one or more alkalinity sources according to the present invention, more preferably between 30 and 50 wt.-%, whereas a liquid laundry detergent composition according to the present invention preferably comprises 3 to 15 wt.-%, more preferably 4 to 10 wt.-%.
  • the alkalinity source preferably is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or mixtures thereof.
  • the composition additionally may comprise additives commonly used in cleaning and/or detergent compositions, preferably selected from the group consisting of pH modifiers, antimicrobial agents, viscosity modifying agents, optical brighteners, organic solvents, bleaching agents, bleach activators, dyes, perfume, membrane-compatible antifoaming agents, corrosion inhibition agents, enzymes, and mixtures thereof.
  • additives commonly used in cleaning and/or detergent compositions preferably selected from the group consisting of pH modifiers, antimicrobial agents, viscosity modifying agents, optical brighteners, organic solvents, bleaching agents, bleach activators, dyes, perfume, membrane-compatible antifoaming agents, corrosion inhibition agents, enzymes, and mixtures thereof.
  • the present invention furthermore provides a method for washing textiles using the composition of the present invention.
  • the method preferably is an automatic machine washing process, wherein waste water accumulated during the whole washing process or parts thereof is purified in a filtration process using one or more membrane filtration units, said filtration process preferably comprising one or more reverse osmosis steps.
  • the above-mentioned compositions are used in commercial laundries.
  • the compositions may as well be used in private washing machines, as a cleaning agent in general and/or a warewashing agent.
  • the inventive composition is membrane-friendly, i.e. it does not cause blocking of the membrane or other damages when it is contained in the waste water which is accumulated during the whole washing process or parts thereof and purified using membrane filtration units.
  • the filtration comprises one or more reverse osmosis steps, which means that the permeation of the wastewater to purify generally remains stable.
  • the obtained purified water may then be reused in another washing cycle, which results in a decrease in the amount of fresh water required to be added to the washing cycle and, accordingly, in a reduction of expenses and in saving resources.
  • Detergent composition were prepared by mixing the compounds listed in table 1 with phosphate or phosphate substitute, respectively, according to table 2.
  • Table 1 Basic Detergent Composition Compound Amount [wt.-% ] C 16 -C 18 fatty alcohol with 14 EO 1 2 C 16 -C 18 fatty alcohol with 6 EO 1 2 C 12 -C 18 coconut fatty acid 3 Alkylbenzene sulfonic acid 2 Hydroxyethylidene diphosphonic acid 1 Sodium hydroxide 2 Sodium carbonate 38 Builder see table 2 Mixture of optical brighteners 0.3 Salts and water remaining In total 100 wt.-% 1 EO: mol ethylene oxides per molecule
  • Table 2 Builder Composition Builder [Amount in wt.-% based on the whole composition] Reference composition 1 26 wt.-% Na 3 PO 4 Reference composition 2 26 wt.-% Na 3 -MGDA Reference composition 3 12 wt.-% sodium salt of a copolymer of maleic acid and acrylic acid Reference composition 4
  • Inventive composition 1 is a solid powdered composition.
  • the composition of the present invention may also be in the form of a liquid composition and table 2 refers to a liquid composition according to the present invention (inventive composition 3).
  • Table 2 Compound Amount [wt.-% ] sodium salt of a copolymer of maleic acid and acrylic acid 6 Na 3 -MGDA 3 C 16 -C 18 fatty alcohol with 14 EO 1 2 C 16 -C 18 fatty alcohol with 6 EO 1 2 C 12 -C 18 coconut fatty acid 3 Alkylbenzene sulfonic acid 2 Hydroxyethylidene diphosphonic acid 0.2 Sodium hydroxide 5 Triethanolamine 2 Propylene Glycol 10 Isopropanol 3 Water 61 Mixture of optical brighteners 0.4 In total 100 wt.-% EO 1
  • reference composition 1 and the inventive composition 1 removal of different fat pigment soil (lanolin, sebum, olive oil, mineral oil, motor oil, make up, and lipstick, respectively) from fabrics made of cotton (CO) and polyester (PES), or a mixture thereof was evaluated.
  • the soiled fabrics were washed for 10 min at 70 °C in a bath comprising 2 g/L of reference composition 1 and the inventive composition 1, respectively, using soft water (0° dH).

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 (12)

  1. Reinigungs- oder Waschmittelzusammensetzung, umfassend
    a) eine oder mehrere Tensidkomponenten, ausgewählt aus der Gruppe bestehend aus:
    (i) alkoxylierten Fettalkoholen der allgemeinen Formel (I) R1O(CnH2nO)xH (I), wobei die Zusammensetzung zwei verschiedene alkoxylierte Fettalkohole umfasst, ein Gemisch aus R1aO(C2H4O)5-7H und R1bO(C2H40)12-16H, worin R1a und R1b gleich oder unterschiedlich sein können und einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 15 bis 20 Kohlenstoffatomen repräsentieren, vorzugsweise mit 16 bis 18 Kohlenstoffatomen,
    (ii) Fettsäuren der allgemeinen Formel (II) R2CO2M (II) und
    (iii) anionischen Tensiden
    oder Gemische davon, wobei R1 und R2 in unabhängiger Weise einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 8 bis 22 Kohlenstoffatomen repräsentieren, n von 1 bis 5 reicht und vorzugsweise 2 oder 3 ist, x den Grad der Alkoxylierung darstellt, reichend von 5 bis 25, und M Wasserstoff oder ein Alkalimetallion repräsentiert;
    b) eine oder mehrere Alkalinitätsquellen,
    c) Wasser, sowie
    d) 5 bis 30 Gew.-%, basierend auf der Gesamtzusammensetzung, an einem Phosphatsubstitut, umfassend
    i) ein wasserlösliches Copolymer, umfassend wenigstens zwei verschiedene aliphatische ungesättigte Monomereinheiten und aufweisend ein Dispergiervermögen für Calciumcarbonat von wenigstens 150 mg CaCO3/g an Copolymer und
    ii) einen mehrzähnigen Chelatbildner, umfassend drei bis sechs komplexierende Gruppen je Molekül und wasserlösliche Komplexe mit Ca2+-Ionen bildend, wobei das Verhältnis von Copolymer zu Chelatbildner im Bereich von größer 1:1 bis 3:1 liegt (Gew.-%/Gew.-%, basierend auf der Gesamtzusammensetzung) und die Zusammensetzung frei ist von jeglichen Phosphaten, Silicaten sowie auf Cellulose basierenden Verbindungen.
  2. Zusammensetzung nach Anspruch 1, umfassend 6 bis 27,5 Gew.-%, vorzugsweise 7,5 bis 25 Gew.-%, und bevorzugter 9 bis 20 Gew.-% an dem Phosphatsubstitut.
  3. Zusammensetzung nach Anspruch 1 oder 2, wobei das Dispergiervermögen des Copolymers für Calciumcarbonat wenigstens 175 mg CaCO3/g an Copolymer beträgt, vorzugsweise wenigstens 200 mg CaCO3/g, bevorzugter wenigstens 250 mg CaCO3/g, und am meisten bevorzugt im Bereich von 280 bis 320 mg CaCO3/g liegt.
  4. Zusammensetzung nach einem der Ansprüche 1 bis 3, wobei die wenigstens zwei unterschiedlichen aliphatischen ungesättigten Monomereinheiten ausgewählt sind aus der Gruppe bestehend aus Acrylsäure, Methacrylsäure, Maleinsäure, Maleinsäureanhydrid und Fumarsäure, oder Salze davon, wobei eine aliphatische ungesättigte Monomereinheit vorzugsweise Maleinsäure ist oder deren Salze, und die zweite aliphatische ungesättigte Monomereinheit vorzugsweise Acrylsäure ist oder deren Salze.
  5. Zusammensetzung nach einem der Ansprüche 1 bis 4, wobei der Chelatbildner eine Polycarbonsäure oder ein Salz davon ist, vorzugsweise ausgewählt aus der Gruppe bestehend aus Hydroxyethylendiamintriessigsäure (HEEDTA), Diethylentriaminpentaessigsäure (DTPA), Methylglycindiessigsäure (MGDA), Glutaminsäure-N,N-diessigsäure (GLDA), Iminodibernsteinsäure (IDHA), Hydroxyiminodibernsteinsäure (HIDS), Ethylendiamindibernsteinsäure (EDDS), Asparaginsäure-N,N-diessigsäure (ASDA), Salze davon sowie Gemische davon.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 5, wobei die Zusammensetzung frei ist von Ethylendiamintetraessigsäure (EDTA), Nitrilotriessigsäure (NTA) und jeglichen siliciumhaltigen Verbindungen.
  7. Zusammensetzung nach Anspruch 1, wobei das anionische Tensid ausgewählt ist aus der Gruppe bestehend aus C8-C18-Alkylsulfaten, C8-C18-Alkylethersulfaten, C8-C18-Alkylsulfonaten, C8-C18-α-Olefinsulfonaten, sulfonierten C8-C18-Fettsäuren, C8-C18-Alkylbenzolsulfonaten, Sulfobernsteinsäuremono- und -di-C1-C12-Estern, C8-C18-Alkylpolyglykolethercarboxylaten, C8-C18-N-Acyltauriden, C8-C18-N-Sarkosinaten, C8-C18-Alkylisethionaten, sowie Gemische davon.
  8. Zusammensetzung nach Anspruch 1 oder 7, wobei die Alkalinitätsquelle ausgewählt ist aus der Gruppe bestehend aus Natriumhydroxid, Kaliumhydroxid, Natriumcarbonat, Kaliumcarbonat, oder Gemische davon, und vorzugsweise vorliegt in einer Menge von 3 bis 90 Gew.-%, bevorzugter in einer Menge von 5 bis 50 Gew.-%, basierend auf der Gesamtzusammensetzung.
  9. Zusammensetzung nach einem der Ansprüche 1 bis 8, wobei die Zusammensetzung zusätzlich Zusatzstoffe umfasst, ausgewählt aus der Gruppe bestehend aus pH-Modifikatoren, antimikrobiellen Mitteln, viskositätsmodifizierenden Mitteln, optischen Aufhellern, organischen Lösemitteln, Bleichmitteln, Bleichaktivatoren, Farbstoffen, Duftstoffen, membrankompatiblen Entschäumern, Korrosionsinhibitoren, Enzymen, sowie Gemische davon.
  10. Verfahren für das Waschen von Textilien unter Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 9.
  11. Verfahren nach Anspruch 10, wobei das während des gesamten Waschvorgangs oder in Teilen desselben angesammelte Abwasser aufbereitet wird in einem Filtrationsverfahren unter Verwendung einer oder mehrerer Membranfiltrationseinheiten, wobei das Filtrationsverfahren vorzugsweise einen oder mehrere Umkehrosmose-Schritte umfasst.
  12. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 9 als Waschmittel in gewerblicher Wäscherei und/oder privaten Waschmaschinen, als Reinigungsmittel und/oder Geschirrspülmittel.
EP09852770.8A 2009-12-30 2009-12-30 Phosphatsubstitute für membrankompatible reinigungs- und/oder waschmittelzusammensetzungen Active EP2519623B2 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2009/055999 WO2011080540A1 (en) 2009-12-30 2009-12-30 Phosphate substitutes for membrane-compatible cleaning and/or detergent compositions

Publications (4)

Publication Number Publication Date
EP2519623A1 EP2519623A1 (de) 2012-11-07
EP2519623A4 EP2519623A4 (de) 2013-06-05
EP2519623B1 true EP2519623B1 (de) 2016-08-03
EP2519623B2 EP2519623B2 (de) 2019-03-20

Family

ID=44226206

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09852770.8A Active EP2519623B2 (de) 2009-12-30 2009-12-30 Phosphatsubstitute für membrankompatible reinigungs- und/oder waschmittelzusammensetzungen

Country Status (3)

Country Link
EP (1) EP2519623B2 (de)
ES (1) ES2598402T5 (de)
WO (1) WO2011080540A1 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8951956B2 (en) 2008-01-04 2015-02-10 Ecolab USA, Inc. Solid tablet unit dose oven cleaner
US9574163B2 (en) 2012-10-26 2017-02-21 Ecolab Usa Inc. Caustic free low temperature ware wash detergent for reducing scale build-up
US9605236B2 (en) 2012-10-26 2017-03-28 Ecolab Usa Inc. Low alkaline low temperature ware wash detergent for protein removal and reducing scale build-up
US9394508B2 (en) 2012-10-26 2016-07-19 Ecolab Usa Inc. Phosphorus free low temperature ware wash detergent for reducing scale build-up
US9267096B2 (en) 2013-10-29 2016-02-23 Ecolab USA, Inc. Use of amino carboxylate for enhancing metal protection in alkaline detergents
KR20160120308A (ko) * 2014-02-13 2016-10-17 바스프 에스이 분말 및 과립, 상기 분말 및 과립의 제조 방법, 및 이의 용도
US9765286B2 (en) 2014-12-22 2017-09-19 Ecolab Usa Inc. Warewashing composition containing alkanol amine phosphonate and methods of use
EP3268347B1 (de) 2015-03-11 2020-05-06 Basf Se Mischungen von chelatbildnern und verfahren zur herstellung dieser mischungen
MY189265A (en) 2015-03-12 2022-01-31 Basf Se Process for making mixtures of enantiomers, and mixtures of enantiomers

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005118760A1 (en) 2004-05-28 2005-12-15 Ecolab Inc. Membrane friendly pasty soap composition
WO2007101470A1 (en) 2006-03-06 2007-09-13 Ecolab Inc. Liquid membrane-compatible detergent composition
EP2083067A1 (de) 2008-01-25 2009-07-29 Basf Aktiengesellschaft Verwendung von organischen Komplexbildnern und/oder polymeren carbonsäuregruppenhaltigen Verbindungen in einer flüssigen Wasch- oder Reinigungsmittelzusammensetzung

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0010247B1 (de) * 1978-10-12 1983-03-23 Henkel Kommanditgesellschaft auf Aktien Phosphatfreies Waschmittel und Verfahren zu dessen Herstellung
EP0021491A1 (de) * 1979-06-18 1981-01-07 THE PROCTER & GAMBLE COMPANY Waschmittelzusammensetzung, die ein nicht-ionisches/kationisches Tensid-Gemisch und ein Builder-Gemisch enthält
DE3472571D1 (en) * 1983-08-27 1988-08-11 Procter & Gamble Detergent compositions
EP0523681B1 (de) * 1991-07-17 1998-11-04 Johannes Dr. Behrensdorf Maschinengeschirrspülmittel und Verfahren zu seiner Herstellung
MXPA01003100A (es) * 1998-09-25 2001-10-01 Zayeed Alam Composiciones detergen
US20050187131A1 (en) * 2004-02-23 2005-08-25 The Procter & Gamble Company Granular laundry detergent composition comprising a ternary detersive surfactant system and low levels of, or no, zeolite builders and phosphate builders
ATE485361T1 (de) * 2005-08-19 2010-11-15 Procter & Gamble Festförmige waschmittelzusammensetzung enthaltend alkylbenzolsulphonat, carbonat-salz und carboxylat-polymer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005118760A1 (en) 2004-05-28 2005-12-15 Ecolab Inc. Membrane friendly pasty soap composition
WO2007101470A1 (en) 2006-03-06 2007-09-13 Ecolab Inc. Liquid membrane-compatible detergent composition
EP2083067A1 (de) 2008-01-25 2009-07-29 Basf Aktiengesellschaft Verwendung von organischen Komplexbildnern und/oder polymeren carbonsäuregruppenhaltigen Verbindungen in einer flüssigen Wasch- oder Reinigungsmittelzusammensetzung

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Dissolvine® GL-47-S", DISSOLVINE DATENBLATT, February 2009 (2009-02-01), pages 1 - 2, XP055362604
"Trilon® M Types", BASF DATENBLATT, May 2007 (2007-05-01), pages 1 - 14, XP055366271

Also Published As

Publication number Publication date
EP2519623A1 (de) 2012-11-07
ES2598402T3 (es) 2017-01-27
ES2598402T5 (es) 2019-10-09
EP2519623B2 (de) 2019-03-20
WO2011080540A1 (en) 2011-07-07
EP2519623A4 (de) 2013-06-05

Similar Documents

Publication Publication Date Title
EP2519623B1 (de) Phosphatsubstitute für membrankompatible reinigungs- und/oder waschmittelzusammensetzungen
US9802884B2 (en) Mixtures of MGDA enantiomers, and process for making such mixtures
EP2571971B1 (de) Reinigungsmittel mit verbesserter fleckenentfernung
RU2676769C2 (ru) Композиции, их получение и применение, и подходящие компоненты
US5733856A (en) Detergency boosting polymer blends as additives for laundry formulations
CN112251301A (zh) 具有铁控制性的持久的酸性洗衣组合物
KR20240018629A (ko) 바이오-기반의 세정제 첨가제
JPH04244094A (ja) アルキルモノグルコシドエーテルカルボキシレート及びアルキルポリグルコシドエーテルカルボキシレート
JP3927623B2 (ja) 洗浄剤組成物
EP4118041A1 (de) Zusammensetzung zur entfernung und verhinderung von kalkablagerungen
KR20170070060A (ko) 아미노카르복시산의 트리알칼리 금속 염의 용액, 이들의 제조 및 용도
CA2295015C (en) Method for washing clothes, in particular working clothes
EP1749081B1 (de) Membranfreundliche pastenförmige seifenzusammensetzung
KR20170127493A (ko) 킬레이트제의 혼합물, 및 이러한 혼합물의 제조 방법
EP2388308A1 (de) Reinigungsmittel mit verbesserter Fleckenentfernung
JPH09250079A (ja) 繊維製品の洗浄方法
EP2855371B1 (de) Zusammensetzung zur wasserenthärtung
US20220010239A1 (en) Detergent polymer and composition
JPH0570795A (ja) 洗浄剤組成物
DE4316743A1 (de) Klarspülmittel mit biologisch abbaubaren Polymeren
NL2004743C2 (en) Cleaning composition with improved stain removal.
JPH0768539B2 (ja) ビリルビン汚れのしみ抜き剤
EP3216781A1 (de) Mischungen die kaliumsalze von methylglycin-diessigsäure enthalten

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: 20120618

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 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)
A4 Supplementary search report drawn up and despatched

Effective date: 20130507

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 3/20 20060101ALI20130430BHEP

Ipc: C11D 3/33 20060101ALI20130430BHEP

Ipc: C11D 3/37 20060101AFI20130430BHEP

17Q First examination report despatched

Effective date: 20150917

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160404

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC 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

Ref country code: AT

Ref legal event code: REF

Ref document number: 817353

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160815

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: 602009040159

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160803

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 817353

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160803

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2598402

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20170127

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: 20160803

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: 20161203

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: 20161103

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: 20160803

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: 20160803

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: 20160803

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

Effective date: 20160803

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: 20160803

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: 20160803

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: 20161205

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: 20160803

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: 20161104

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

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: 20160803

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: 20160803

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602009040159

Country of ref document: DE

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: 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: 20160803

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: 20160803

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: 20160803

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: 20160803

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: 20160803

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: 20161103

26 Opposition filed

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20170503

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: CH

Ref legal event code: PL

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: 20160803

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: 20160803

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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

Ref country code: LU

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

Effective date: 20161230

Ref country code: CH

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

Effective date: 20161231

Ref country code: LI

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

Effective date: 20161231

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: IE

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

Effective date: 20161230

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: 20160803

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: 20091230

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: 20160803

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: 20160803

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 NON-PAYMENT OF DUE FEES

Effective date: 20161230

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20190320

AK Designated contracting states

Kind code of ref document: B2

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

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 602009040159

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Ref document number: 2598402

Country of ref document: ES

Kind code of ref document: T5

Effective date: 20191009

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

Effective date: 20230503

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

Ref country code: ES

Payment date: 20250117

Year of fee payment: 16

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

Ref country code: DE

Payment date: 20251104

Year of fee payment: 17

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

Ref country code: GB

Payment date: 20251114

Year of fee payment: 17

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

Ref country code: IT

Payment date: 20251121

Year of fee payment: 17

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

Ref country code: FR

Payment date: 20251110

Year of fee payment: 17