EP1854869B2 - Sachet contenant du liquide, soluble dans l'eau - Google Patents

Sachet contenant du liquide, soluble dans l'eau Download PDF

Info

Publication number
EP1854869B2
EP1854869B2 EP06113694.1A EP06113694A EP1854869B2 EP 1854869 B2 EP1854869 B2 EP 1854869B2 EP 06113694 A EP06113694 A EP 06113694A EP 1854869 B2 EP1854869 B2 EP 1854869B2
Authority
EP
European Patent Office
Prior art keywords
water
liquid composition
soluble
pouch
soluble pouch
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
EP06113694.1A
Other languages
German (de)
English (en)
Other versions
EP1854869B1 (fr
EP1854869A1 (fr
Inventor
Francesco De Buzzaccarini
Steven Jozef Louis Coosemans
Lorenzo Matteo Pierre Gualco
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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=37188984&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1854869(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to PL06113694T priority Critical patent/PL1854869T5/pl
Priority to ES06113694.1T priority patent/ES2363525T5/es
Priority to AT06113694T priority patent/ATE502999T1/de
Priority to EP06113694.1A priority patent/EP1854869B2/fr
Priority to DE602006020845T priority patent/DE602006020845D1/de
Priority to CA2608882A priority patent/CA2608882C/fr
Priority to PCT/US2006/021044 priority patent/WO2006130647A1/fr
Priority to JP2008513839A priority patent/JP2008545590A/ja
Publication of EP1854869A1 publication Critical patent/EP1854869A1/fr
Publication of EP1854869B1 publication Critical patent/EP1854869B1/fr
Priority to JP2011264842A priority patent/JP5694132B2/ja
Publication of EP1854869B2 publication Critical patent/EP1854869B2/fr
Application granted granted Critical
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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

  • the present invention relates to water-soluble, liquid-containing pouches, especially to pouches containing cleaning liquids such as detergents and hard surface cleaners. More specifically, the invention is directed to water-soluble pouches which exhibit improved compatibility when used in combination with selected levels of water and ionic components selected from the group consisting of carboxylates, phosphonates, and mixtures thereof, and a magnesium salt.
  • Liquid-filled pouches are known as a convenient form of packaging consumer products as well as industrial products.
  • the liquid can be provided in premeasured quantities intended for use as "unit doses".
  • the film enveloping the liquid product, which forms the wall of the pouch, is soluble in water.
  • a particularly suitable water-soluble film for this purpose is made from polyvinyl alcohol, and, in this context, this invention is particularly suited to packaging unit doses of liquid detergent.
  • Commonly known water-soluble pouches are generally formed by using either a vertical form-fill-seal (VFFS) or horizontal form-fill-seal (HFFS) processes or by directly thermoforming water soluble envelopes.
  • VFFS vertical form-fill-seal
  • HFFS horizontal form-fill-seal
  • Liquid products have been packaged in water-soluble films wherein the film is made from a water-soluble co-polymer comprising vinyl alcohol and carboxylic acid groups.
  • most of such water-soluble films exhibit poor compatibility when used in combination with compositions packed therein and comprising dissolved ionic components selected from the group consisting of carboxylates, phosphonates, and mixtures thereof.
  • Such ionic components are desirable in liquid detergents as they generally act as builders or chelants.
  • the aforementioned incompatibility translates into a substantial solubility loss of water-soluble pouches made from a film comprising a co-polymer of vinyl alcohol and a carboxylic acid.
  • WO 01/79417 discloses a water-soluble package formed from a polymeric film, containing a non-aqueous liquid composition comprising an ionic ingredient and an excess of a stabilizing compound which is allegedly effective for reducing the formation of lactones within the film.
  • US 6,185,410 describes a pouch made of a water-soluble film, containing a liquid composition comprising a solid builder/chelant and an anionic surfactant.
  • WO 2004/085586 discloses a water-soluble pouch containing a liquid comprising dissolved ionic components selected from the group of carboxylates, phosphonates and mixtures thereof, and wherein the pouch is manufactured from a water-soluble film which has been specifically modified.
  • a liquid-containing water-soluble pouch comprising dissolved ionic components selected from the group consisting of carboxylates, phosphonates, and mixtures thereof and a magnesium salt and wherein said pouch is made by using a horizontal form-fill-seal process (HFFS) and comprises a liquid composition having a carefully selected level of water.
  • HFFS horizontal form-fill-seal process
  • the water-soluble liquid-containing pouch according to the present invention provides enhanced dissolution and disintegration profiles even after prolonged storage. Additionally, as the water-soluble pouches of the instant invention provide stable dissolution of the ionic components, the latter may perform their function with a significant improvement and fewer amounts of such components may be required.
  • a further advantage of the water-soluble pouches according to the present invention is that they may be manufactured using commercially available water-soluble films without any further modifications required.
  • the present invention encompasses a water-soluble pouch containing a liquid composition
  • the water-soluble pouch is made from a film comprising a co-polymer of vinyl alcohol and a carboxylic acid
  • the liquid composition contained within said pouch comprises at least one dissolved ionic component selected from the group consisting of carboxylates, phosphonates and mixtures thereof, and from 5% to 15 % by weight of the liquid composition of water and a magnesium salt and wherein said pouch is processed using a vacuum formed, horizontal form-fill-seal process.
  • the present invention encompasses a process for making a water-soluble pouch having improved water-solubility upon storage, wherein the process comprises the steps of (a) formulating a liquid composition comprising at least one dissolved ionic component selected from the group consisting of carboxylates, phosphonates and mixtures thereof, and from 5% to 15 % by weight of the liquid composition of water and a magnesium salt and (b) processing a film comprising a copolymer of vinyl alcohol and a carboxylic acid into a water-soluble pouch containing the liquid composition using a vacuum formed, horizontal form-fill-seal process.
  • the water-soluble film comprises a co-polymer of vinyl alcohol and a carboxylic acid.
  • the level of the co-polymer in the film material is at least 60% by weight of the film.
  • the polymer can have any weight average molecular weight, preferably from 1000 daltons to 1,000,000 daltons, more preferably from 10,000 daltons to 300,000 daltons, even more preferably from 15,000 daltons to 200,000 daltons, most preferably from 20,000 daltons to 150,000 daltons.
  • the co-polymer present in the film is from 60% to 98% hydrolysed, more preferably 80% to 95% hydrolysed, to improve the dissolution of the material.
  • the co-polymer comprises from 0.1 mol% to 30 mol%, preferably from 1 mol% to 6 mol%, of said carboxylic acid.
  • the water-soluble film of the present invention may further comprise additional co-monomers.
  • additional co-monomers include sulphonates and ethoxylates.
  • An example of preferred sulphonic acid is 2-acrylamido-2-methyl-1-propane sulphonic acid (AMPS).
  • a suitable water-soluble film for use in the context of the present invention is commercially available under tradename M8630 TM from Mono-Sol of Indiana, US.
  • the water-soluble film herein may also comprise ingredients other than the polymer or polymer material.
  • plasticisers for example glycerol, ethylene glycol, diethyleneglycol, propane diol, 2-methyl-1,3-propane diol, sorbitol and mixtures thereof, additional water, disintegrating aids, fillers, anti-foaming agents, emulsifying/dispersing agents, and/or antiblocking agents.
  • the pouch or water-soluble film itself comprises a detergent additive to be delivered to the wash water, for example organic polymeric soil release agents, dispersants, dye transfer inhibitors.
  • the surface of the film of the pouch may be dusted with fine powder to reduce the coefficient of friction.
  • Sodium alumino silicate, silica, talc and amylose are examples of suitable fine powders.
  • liquid is used herein to broadly include, for example, mixtures, solutions, dispersions and emulsions, although homogeneous liquids are most preferred.
  • the liquid may have from low to very high viscosities including gels and pastes.
  • the preferred viscosity may be up to 10,000 mPa.s, but it is more preferably from 100 to 3000 mPa.s, and most preferably from 300 to 1500 mPa.s when measured at 20 sec-1 and 21°C.
  • the liquid may contain active ingredients suitable for various applications. Examples of such applications are domestic and consumer products, e.g. laundry cleaning and treatment, dish and hard surface cleaning, shampoo, bath additives; agrochemicals, e.g.
  • liquids are suitable for use as liquid detergents in the cleaning of clothes, dishes, and other household surfaces.
  • the liquid composition preferably has a density of 0.8 kg/l to 1.3 kg/l, preferably about 1.0 to 1.1 kg/l.
  • the liquid composition can be made by any method and can have any viscosity, typically depending on its ingredients. The viscosity may be controlled, if desired, by using various viscosity modifiers such as hydrogenated castor oil and/or solvents. Hydrogenated castor oil is commercially available as Thixcin ® . Suitable solvents are described in more detail below.
  • liquid compositions of the present invention are homogeneous solutions and, in particular, that the ionic components are dissolved in the homogeneous liquid.
  • the liquid of the present invention preferably has a pH of less than 9, preferably less than 8, when measured by dissolving the liquid to a level of 1% in demineralized water.
  • the liquid compositions of the present invention comprise at least one dissolved ionic component selected from the group consisting of carboxylates, phosphonates, and mixtures thereof Such ionic components may be suitable as builder/chelant actives used for binding metal ions in aqueous solutions.
  • the ionic component is a carboxylate, preferably a carboxylate builder, even more preferably a polycarboxylate builder.
  • carboxylate as used herein encompasses the acid form of the salt and also encompasses "polycarboxylate” which refers to compounds having a plurality of carboxylate groups, preferably at least three carboxylates.
  • Suitable polycarboxylate builder can preferably be added to the composition in acid form, but can also be added in the form of a neutralized salt.
  • alkali metals such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964 , and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972 . See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987 .
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679 ; 3,835,163 ; 4,158,635 ; 4,120,874 and 4,102,903 .
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C 5 -C 20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in EP-A-0 200 263, published November 5, 1986 .
  • nitrogen-containing, phosphor-free aminocarboxylates include ethylene diamine disuccinic acid and salts thereof (ethylene diamine disuccinates, EDDS), ethylene diamine tetraacetic acid and salts thereof (ethylene diamine tetraacetates, EDTA), and diethylene triamine penta acetic acid and salts thereof (diethylene triamine penta acetates, DTPA).
  • polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967 . See also Diehl U.S. Patent 3,723,322 .
  • Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • the ionic component is a phosphonate component.
  • phosphonate as used herein encompasses the acid form of the salt.
  • Suitable phosphonates for use in the present invention may be selected from the group of inorganic and organic phosphonates.
  • the phosphonate is selected from organic phosphonates.
  • suitable organic phosphonates for use herein are amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy bisphosphonates and nitrilo trimethylene phosphonates.
  • Preferred organic phosphonates for use herein are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate (HEDP). In the context of the present invention, HEDP is highly preferred.
  • said at least one ionic component may be incorporated at a level of from 0.2% to 4.0%, preferably from 0.5% to 3.0%, more preferably from 0.5% to 2.0% by weight of the liquid composition.
  • liquid compositions of the present invention are concentrated compositions, they still contain some amount of water.
  • the liquid composition contained within the water-soluble liquid-containing pouches according to the present invention shall, as a first essential requirement, comprise, with increasing preference in the order given, from 5%, 6%, 7%, 8%, 9% to, with increasing preference in the order given, 15 %, 14%, 13%, 12%, 11%, 10% by weight of the liquid composition, of water.
  • the liquid composition contained within the water-soluble liquid-containing pouch according to the present invention shall comprise from 5% to 15%, preferably from 6% to 12 %, more preferably from 7% to 10%, most preferably from 8% to 10% by weight of the liquid composition, of water.
  • the water-soluble liquid-containing pouches according to the present invention shall be processed using a vacuum formed, horizontal form-fill-seal process (HFFS).
  • HFFS horizontal form-fill-seal process
  • Pouches according to the present invention may be processed according to any of the horizontal form-fill-seal methods commonly know in the art. A suitable method is described for example in WO 02/60758 .
  • a suitable HFFS process to form the water-soluble liquid-containing pouches of the present invention is a continuous process comprising the steps of: (a) continuously feeding a first water-soluble film onto a horizontal portion of a continuously and rotatably moving endless surface, which comprises a plurality of moulds; (b) forming from the film on the horizontal portion of the continuously moving surface, and in the moulds on the surface, a continuously moving, horizontally positioned web of open pouches, by application of a vacuum through the bottom of the moulds onto the film; (c) filling the continuously moving, horizontally positioned web of open pouches with a liquid, to obtain a horizontally positioned web of open, filled pouches; (d) continuously closing the web of open pouches, to obtain closed pouches, by feeding a second water-soluble film onto the horizontally positioned web of open, filed pouches; and (e) heat sealing the closed pouches.
  • step (e) above may be performed by solvent welding (as described in WO 03/008486 ), and solvent or wet sealing.
  • the first water-soluble film While using a vacuum formed, horizontal form-fill-seal process, the first water-soluble film will typically have a thickness of from 20 ⁇ m to 100 ⁇ m before thermoforming.
  • the liquid composition also comprises a magnesium salt.
  • a metal salt further contributes in obtaining stable dissolution of the ionic components into the liquid composition contained within the water-soluble pouches according to the invention.
  • Particularly preferred salts are magnesium chloride, magnesium sulphate, magnesium sulfite and magnesium bisulfite.
  • Magnesium chloride is a highly preferred salt in the context of the present invention. However the Applicant has found that chloride ions, especially at high temperatures, can have long term detrimental effects on the manufacturing equipment. In this case the most preferred metal salt is magnesium bisulfite.
  • the use of magnesium bisulfite brings further advantages as well. Potassium sulfite provides a known benefit of improving the aesthetics of a composition upon ageing. The use of magnesium bisulfite, allows the detergent manufacturer to gain two benefits from one ingredient. Magnesium stabilizes the dissolved ionic component and the bisulfite provides the aesthetic benefit described above:
  • liquid composition is a detergent composition
  • at least a surfactant and/or a builder be present, preferably at least an anionic surfactant and preferably also a nonionic surfactant, and preferably at least a builder, more preferably at least a water-soluble builder such as phosphate builder and/or fatty acid builder.
  • Other preferred components are enzymes and/or bleaching agents, such as a preformed peroxyacid.
  • perfumes are also perfume, brightener, buffering agents, fabric softening agents, including clays and silicones, benefit agents, and suds suppressors.
  • a water-soluble builder is present, such as a phosphate, and preferably also surfactant, perfume, enzymes, bleach.
  • a perfume and a fabric benefit agent are present for example a cationic softening agent, silicone softening agent or clay softening agent, anti-wrinkling agent, fabric substantive dye.
  • compositions of the invention are preferably concentrated liquids having preferably less than 50% or even less than 40% by weight of solvent (other than water), preferably less than 30% or even less than 20% by weight of solvent (other than water).
  • solvent is present at a level of at least 5% or even at least 10% or even at least 15% by weight of the composition.
  • the composition comprises a plasticiser for the water-soluble pouch material, for example one of the plasticisers described above, for example glycerol.
  • plasticisers can have the dual purpose of being a solvent for the other ingredients of the composition and a plasticiser for the pouch material.
  • ionic ingredients selected from the group of polycarboxylated polymers (such as polyacrylic acid, polyacrylic-maleic acid copolymers), cationic ethoxylated amines, zwiterrionic polymers (such as those described in EP patent application No. 04447256 ), anionic soil release polymers.
  • polycarboxylated polymers such as polyacrylic acid, polyacrylic-maleic acid copolymers
  • cationic ethoxylated amines such as those described in EP patent application No. 04447256
  • anionic soil release polymers such as those described in EP patent application No. 04447256
  • a process for making a water-soluble pouch having improved water-solubility upon storage comprising the steps of (a) formulating a liquid composition comprising at least one dissolved ionic component selected from the group consisting of carboxylates, phosphonates and mixtures thereof, and from 5% to 15 % by weight of the liquid composition of water, and (b) processing a film comprising a copolymer of vinyl alcohol and a carboxylic acid into a water-soluble pouch containing said liquid composition, using a vacuum formed, horizontal form-fill-seal process.
  • the method provides a relative assessment of the solubility of liquid detergent pouches under specified consumer relevant conditions. Data are generated by visual grading of PVA residues, relative to a defined grading scale.
  • Liquid detergent-containing PVA pouches (at recommended dosage for normal conditions) are added, in a standardized way, inside the black velvet pouches. The resulting black pouches are thereafter closed by stitching. Each of the 4 washing machines is loaded with 4 black pouches in a standardized way. Different liquid detergent pouches may be added into a single washing machine, however at least 4 external replicates for each of the products are needed.
  • Test conditions wool wash program at 40°C, using city water of 14°C +/- 1°C via the water temperature control system.
  • Visual grading At the end of the washing cycle, the black pouches are opened and visual grading of the polymer residues on fabric is immediately performed by at least 2 persons, according to a pre-defined grading scale.
  • the overall grade is a statistical average of the different replicates.
  • the grading scale ranges from 0, meaning no noticeable PVA residues on fabric after the wash, to 7, meaning that substantially no PVA pouch is noticeably dissolved.
  • good pouch dissolution is obtained for a score below 3.
  • a score of 3 means that no opaque PVA residues with a largest average diameter greater than 2 cm are visible on fabric after the wash. Ideally, the score should be as low as possible.
  • compositions are made by combining the listed ingredients in the listed proportions (weight % unless otherwise specified).
  • Example compositions 1 to 4 are meant to exemplify compositions according to the present invention but are not necessarily used to limit or otherwise define the scope of the present invention.
  • Dodecylbenzene sulphonic acid is commercially available from Ifrachem.
  • C12-14 alcohol, 7x ethoxylated is commercially available from Sasol.
  • C8-C10 amido propyl dimethylamine is commercially available from Akzo Nobel Chemicals LTD.
  • Citric acid is commercially available from Citrique Belge NV.
  • C12-C18 alkyl fatty acid is commercially available from Akzo Nobel Chem. GMBH.
  • Hydroxyethane diphosphonic acid is commercially available from Solutia Europe NV.
  • Diethylene Triamine Penta methylene phosponic acid is commercially available from Albright & Wilson LTD.
  • Enzymes are proteolitic and amylolytic enzyme solutions commercially available from respectively Genencor and Novozymes.
  • Magnesium chloride is commercially available from Nedmag. Potassium sulfite is commercially available from BASF.
  • Polyethyleneimine ethoxylate PEI600 E20 is commercially available from BASF.
  • Zwitterionic polyamine is Lutensit Z96 TM , commercially available from BASF.
  • Optical brightener is disodium 4,4'-bis-(2-sulphostyryl) biphenyl, commercially available from Ciba AG.
  • Hydrogenated castor oil is commercially available from Brazil Oleo De Mamona.
  • Propylene glycol is commercially available from BASF.
  • Glycerine is commercially available from NAT OLEO. Polydimethylsiloxane is commercially available from Dow Coming. Monoethanolamine is commercially available from Sasol.
  • the liquid compositions 1, 2, 3 and 4 were packed into film pouches using vacuum-formed, horizontal form-fill-seal process, each pouch containing about 50 ml of liquid.
  • the film was made from a polyvinyl alcohol / carboxylate copolymer resin (M8630 TM , Mono-Sol, Indiana, US).
  • the resulting pouches comprise completely homogeneous liquids.
  • the dissolution and disintegration profiles of each of the pouched compositions is good; the pouches dissolve/disintegrate rapidly in water without leaving any residue even after prolonged storage (eight weeks) at 35°C.
  • Example compositions are made by combining the listed ingredients in the listed proportions (weight % unless otherwise specified).
  • Example composition 5 is meant to exemplify compositions according to the present invention but is not necessarily used to limit or otherwise define the scope of the present invention.
  • Example compositions A, B , and C are comparative examples.
  • Example composition 6 is a reference example, which is outside the scope of the claims.
  • Formic acid is commercially available from BASF.
  • Ethoxylated tetraethylene pentamine is commercially available from BASF.
  • Optical brightener is disodium 4,4'-bis-(2-sulphostyryl) biphenyl, commercially available as from Ciba AG, in compositions 5 and B and is a disulphated di-amino stilbene based fluorescent whitening agent, commercially available from Hickson & Welch LTD, in compositions 6, A and C.
  • the liquid compositions 5, A, and B were packed into film pouches using vacuum-formed, horizontal form-fill-seal process, each pouch containing about 50ml of liquid.
  • the film was made from a polyvinyl alcohol / carboxylate copolymer resin (sold under the trade reference M8630 TM by Mono-Sol of Indiana, US).
  • the corresponding pouches were stored for 8 weeks at 35°C.
  • the physical stability after storage has been assessed by visual observation of the corresponding pouches.
  • the in-wash solubility of the liquid-containing pouches has been assessed using the "Black Pouch Solubility Method" as described herein above. Results are presented in the table below.
  • Pouched composition 5 Pouched composition A
  • Pouched composition B Physical stability Translucent, homogeneous Solid precipitate of HEDP present Translucent, Homogeneous Black pouch solubility score 1.5 (good solubility) n.a. 3.6 (poor solubility)
  • Liquid compositions 6 and C have the same chemical composition but were packed into two different types of film pouches, both containing about 50ml of liquid composition but processed using two different manufacturing processes.
  • a first set of pouches was manufactured using vacuum-formed, horizontal form-fill-seal process (HFFS) (pouched composition 6 ), and a second set of pouches was manufactured using vertical form-fill-seal process (VFFS) (pouched composition C ).
  • the films were made from a polyvinyl alcohol / carboxylate copolymer resin (commercially available under tradename M8630 TM from Mono-Sol of Indiana, US). The corresponding pouches were stored for 10 months at room temperature.

Landscapes

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

Claims (10)

  1. Sachet hydrosoluble contenant une composition liquide, dans lequel le sachet hydrosoluble est fabriqué à partir d'un film comprenant un copolymère d'alcool vinylique et un acide carboxylique, dans lequel la composition liquide contenue au sein dudit sachet comprend au moins un composant ionique dissous choisi dans le groupe constitué de carboxylates, de phosphonates et leurs mélanges, caractérisé en ce que ladite composition liquide comprend de 5 % à 15 % en poids de la composition liquide d'eau et d'un sel de magnésium, et ledit sachet est réalisé en utilisant un procédé de formage-remplissage-scellage horizontal formé sous vide.
  2. Sachet hydrosoluble selon la revendication 1, dans lequel ledit au moins un composant ionique est un phosphonate.
  3. Sachet hydrosoluble selon la revendication 2, dans lequel ledit au moins un composant ionique est l'hydroxy-éthylène 1,1 diphosphonate.
  4. Sachet hydrosoluble selon l'une quelconque des revendications précédentes, dans lequel ladite composition liquide comprend de 6 % à 12 %, de préférence de 7 % à 10 %, plus préférablement de 8 % à 10 % en poids de la composition liquide, d'eau.
  5. Sachet hydrosoluble selon l'une quelconque des revendications précédentes, dans lequel ladite composition liquide comprend de 0,2 % à 4,0 %, de préférence de 0,5 % à 3,0 %, plus préférablement de 0,5 % à 2,0 % en poids de la composition liquide, dudit au moins un composant ionique.
  6. Sachet hydrosoluble selon la revendication 1, dans lequel ledit sel de magnésium est choisi parmi le chlorure de magnésium, le bisulfite de magnésium ou leurs mélanges
  7. Sachet hydrosoluble selon la revendication 6, dans lequel ladite composition liquide comprend moins de 1 %, de préférence moins de 0,5 %, plus préférablement moins de 0,3 % en poids de la composition liquide, desdits sels métalliques.
  8. Sachet hydrosoluble selon l'une quelconque des revendications précédentes, dans lequel ladite composition liquide comprend en outre un ou plusieurs ingrédients choisis parmi le groupe des acides polycarboxyliques, des sels de polycarboxylate, des acides polyphosphoniques, des sels de polyphosphonate, des amines éthoxylées cationiques, des polymères zwittérioniques, des enzymes, et leurs mélanges.
  9. Sachet hydrosoluble selon l'une quelconque des revendications précédentes, dans lequel ledit sachet après un stockage de 8 semaines à 35 °C présente une hydrosolubilité selon le « procédé de solubilité du sachet noir » de telle sorte qu'aucun résidu de film avec un diamètre moyen le plus grand supérieur à 2 cm n'est visible sur le tissu après lavage.
  10. Procédé de fabrication d'un sachet hydrosoluble ayant une hydrosolubilité améliorée lors du stockage, dans lequel ledit procédé comprend les étapes consistant à :
    (a) formuler une composition liquide comprenant au moins un composant ionique dissous choisi dans le groupe constitué de carboxylates, phosphonates et leurs mélanges de 5 % à 15 % en poids de la composition liquide d'eau et d'un sel de magnésium et ;
    (b) traiter un film comprenant un copolymère d'alcool vinylique et un acide carboxylique en un sachet hydrosoluble contenant ladite composition liquide, en utilisant un procédé de formage-remplissage-scellage horizontal formé sous vide.
EP06113694.1A 2005-06-01 2006-05-09 Sachet contenant du liquide, soluble dans l'eau Active EP1854869B2 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
PL06113694T PL1854869T5 (pl) 2006-05-09 2006-05-09 Rozpuszczalny w wodzie woreczek zawierający ciecz
ES06113694.1T ES2363525T5 (es) 2006-05-09 2006-05-09 Bolsa que contiene líquido soluble en agua
AT06113694T ATE502999T1 (de) 2006-05-09 2006-05-09 Flüssigkeitsgefüllter wasserlöslicher beutel
EP06113694.1A EP1854869B2 (fr) 2006-05-09 2006-05-09 Sachet contenant du liquide, soluble dans l'eau
DE602006020845T DE602006020845D1 (de) 2006-05-09 2006-05-09 Flüssigkeitsgefüllter wasserlöslicher Beutel
PCT/US2006/021044 WO2006130647A1 (fr) 2005-06-01 2006-05-31 Sachet hydrosoluble contenant un liquide
CA2608882A CA2608882C (fr) 2005-06-01 2006-05-31 Sachet hydrosoluble contenant un liquide
JP2008513839A JP2008545590A (ja) 2005-06-01 2006-05-31 水溶性液体収容パウチ
JP2011264842A JP5694132B2 (ja) 2005-06-01 2011-12-02 水溶性液体収容パウチ

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP06113694.1A EP1854869B2 (fr) 2006-05-09 2006-05-09 Sachet contenant du liquide, soluble dans l'eau

Publications (3)

Publication Number Publication Date
EP1854869A1 EP1854869A1 (fr) 2007-11-14
EP1854869B1 EP1854869B1 (fr) 2011-03-23
EP1854869B2 true EP1854869B2 (fr) 2014-12-03

Family

ID=37188984

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06113694.1A Active EP1854869B2 (fr) 2005-06-01 2006-05-09 Sachet contenant du liquide, soluble dans l'eau

Country Status (5)

Country Link
EP (1) EP1854869B2 (fr)
AT (1) ATE502999T1 (fr)
DE (1) DE602006020845D1 (fr)
ES (1) ES2363525T5 (fr)
PL (1) PL1854869T5 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8772220B2 (en) 2007-08-24 2014-07-08 Sekisui Specialty Chemicals America, Llc Chemical delivery product and process for making the same
DE102012201502A1 (de) * 2012-02-02 2013-08-08 Henkel Ag & Co. Kgaa Wasserarmes, flüssiges Waschmittel mit erhöhter Fettlösekraft
US20140323383A1 (en) 2013-04-26 2014-10-30 The Procter & Gamble Company Pouch comprising a liquid detergent composition
EP3279302A1 (fr) * 2016-08-04 2018-02-07 The Procter & Gamble Company Article de dose unitaire soluble dans l'eau comprenant de l'huile de ricin hydrogénée

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002012432A1 (fr) † 2000-08-08 2002-02-14 The Procter & Gamble Company Composition liquide
WO2002074893A1 (fr) † 2001-03-16 2002-09-26 The Procter & Gamble Company Produit detergent
WO2002094975A1 (fr) † 2001-05-22 2002-11-28 The Procter & Gamble Company Compositions en sachets
WO2003089563A2 (fr) † 2002-04-19 2003-10-30 Colgate-Palmolive Company Systeme nettoyant comprenant une composition de nettoyage liquide placee dans un contenant hydrosoluble
WO2004085586A2 (fr) † 2003-03-19 2004-10-07 The Procter & Gamble Company Poche contenant du liquide soluble dans l'eau
WO2006088980A1 (fr) † 2005-02-17 2006-08-24 The Procter & Gamble Company Composition de soin de tissus

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3128287A (en) 1963-01-31 1964-04-07 Pfizer & Co C 2,2'-oxodisuccinic acid, derivatives thereof, and process for preparing
US3308067A (en) 1963-04-01 1967-03-07 Procter & Gamble Polyelectrolyte builders and detergent compositions
US3635830A (en) 1968-05-24 1972-01-18 Lever Brothers Ltd Detergent compositions containing oxydisuccing acid salts as builders
US3723322A (en) 1969-02-25 1973-03-27 Procter & Gamble Detergent compositions containing carboxylated polysaccharide builders
US3835163A (en) 1973-08-02 1974-09-10 Monsanto Co Tetrahydrofuran polycarboxylic acids
US4102903A (en) 1977-01-05 1978-07-25 Monsanto Company Tetrahydropyran and 1,4-dioxane polycarboxylate compounds, methods for making such compounds and compositions and methods employing same
US4120874A (en) 1977-01-05 1978-10-17 Monsanto Company Diesters of 6-cyano-2,2-tetrahydropyrandicarboxylates
US4144226A (en) 1977-08-22 1979-03-13 Monsanto Company Polymeric acetal carboxylates
US4158635A (en) 1977-12-05 1979-06-19 Monsanto Company Detergent formulations containing tetrahydropyran or 1,4-dioxane polycarboxylates and method for using same
US4566984A (en) 1984-11-16 1986-01-28 The Procter & Gamble Company Ether polycarboxylates
GB8511303D0 (en) 1985-05-03 1985-06-12 Procter & Gamble Liquid detergent compositions
US4663071A (en) 1986-01-30 1987-05-05 The Procter & Gamble Company Ether carboxylate detergent builders and process for their preparation
US20030148914A1 (en) * 2001-10-29 2003-08-07 The Procter & Gamble Company Detergent system
ES2244828T3 (es) * 2001-12-14 2005-12-16 Unilever N.V. Envase soluble en agua con detergente liquido en capas para colada.
ATE318541T1 (de) * 2002-05-24 2006-03-15 Procter & Gamble Waschmittelsystem
EP1431381A1 (fr) * 2002-12-19 2004-06-23 The Procter & Gamble Company Produit pour le traitement de tissus à dose unitaire, à compartiment unique et comprenant des compositions ensachées avec des agents adoucissants cationiques
US7022656B2 (en) * 2003-03-19 2006-04-04 Monosol, Llc. Water-soluble copolymer film packet

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002012432A1 (fr) † 2000-08-08 2002-02-14 The Procter & Gamble Company Composition liquide
WO2002074893A1 (fr) † 2001-03-16 2002-09-26 The Procter & Gamble Company Produit detergent
WO2002094975A1 (fr) † 2001-05-22 2002-11-28 The Procter & Gamble Company Compositions en sachets
WO2003089563A2 (fr) † 2002-04-19 2003-10-30 Colgate-Palmolive Company Systeme nettoyant comprenant une composition de nettoyage liquide placee dans un contenant hydrosoluble
WO2004085586A2 (fr) † 2003-03-19 2004-10-07 The Procter & Gamble Company Poche contenant du liquide soluble dans l'eau
WO2006088980A1 (fr) † 2005-02-17 2006-08-24 The Procter & Gamble Company Composition de soin de tissus

Also Published As

Publication number Publication date
PL1854869T5 (pl) 2015-06-30
ATE502999T1 (de) 2011-04-15
ES2363525T3 (es) 2011-08-08
PL1854869T3 (pl) 2011-08-31
DE602006020845D1 (de) 2011-05-05
EP1854869B1 (fr) 2011-03-23
ES2363525T5 (es) 2015-03-23
EP1854869A1 (fr) 2007-11-14

Similar Documents

Publication Publication Date Title
CA2608882C (fr) Sachet hydrosoluble contenant un liquide
US20060275566A1 (en) Water-soluble, liquid-containing pouch
EP1604005B1 (fr) Poche contenant du liquide soluble dans l'eau
US20060063691A1 (en) Water-soluble, liquid-containing pouch
EP1516917B1 (fr) Composition détergente sous forme de dose unitaire liquide
CA2420372C (fr) Recipients thermoformes hydrosolubles comprenant des compositions aqueuses
GB2374581A (en) Water-soluble containers
US20040063601A1 (en) Method for manufacturing liquid gel automatic dishwashing detergent compositions comprising anhydrous solvent
US20040067861A1 (en) Liquid gel automatic dishwashing detergent composition comprising anhydrous solvent
US6943143B2 (en) Detergent composition
EP1854869B2 (fr) Sachet contenant du liquide, soluble dans l'eau
PL204786B1 (pl) Produkt detergentowy obejmujący ciekłą kompozycję detergentową opakowaną w materiał opakowaniowy oraz jego zastosowanie
US20140057822A1 (en) Container
US20140315776A1 (en) Container for use in a washing process
DE10313453A1 (de) Portionierte Wasch- oder Reinigungsmittelzusammensetzung
EP2892992B1 (fr) Composition de détergent emballée

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

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20080429

17Q First examination report despatched

Effective date: 20080604

AKX Designation fees paid

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

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602006020845

Country of ref document: DE

Date of ref document: 20110505

Kind code of ref document: P

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006020845

Country of ref document: DE

Effective date: 20110505

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

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

Ref country code: LT

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

Effective date: 20110323

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: 20110323

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: 20110323

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: 20110624

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2363525

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20110808

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20110323

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: 20110323

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: 20110323

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: 20110323

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: 20110323

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: 20110623

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

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

Ref country code: 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: 20110725

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: 20110323

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E011551

Country of ref document: HU

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

Ref country code: SK

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

Effective date: 20110323

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: 20110323

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: 20110723

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20111119

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

Ref country code: MC

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

Effective date: 20110531

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26 Opposition filed

Opponent name: RECKITT BENCKISER (UK) LIMITED

Effective date: 20111221

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20111119

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

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

Free format text: ORIGINAL CODE: EPIDOSNOBS2

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: 20110531

Ref country code: CH

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

Effective date: 20110531

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602006020845

Country of ref document: DE

Effective date: 20111119

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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: 20110509

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

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

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 502999

Country of ref document: AT

Kind code of ref document: T

Effective date: 20110323

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: 20110509

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: 20110323

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

Ref country code: NL

Payment date: 20140513

Year of fee payment: 9

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: 20141203

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 HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 602006020845

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 602006020845

Country of ref document: DE

Effective date: 20141203

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Ref document number: 2363525

Country of ref document: ES

Kind code of ref document: T5

Effective date: 20150323

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20141203

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: 20141203

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

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: 20141203

REG Reference to a national code

Ref country code: PL

Ref legal event code: T5

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

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

Ref country code: CZ

Payment date: 20160428

Year of fee payment: 11

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

Ref country code: IT

Payment date: 20160518

Year of fee payment: 11

Ref country code: PL

Payment date: 20160602

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

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

Ref country code: HU

Payment date: 20170424

Year of fee payment: 12

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 NON-PAYMENT OF DUE FEES

Effective date: 20170509

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

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: 20170509

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 NON-PAYMENT OF DUE FEES

Effective date: 20180510

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

Ref country code: PL

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

Effective date: 20170509

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 18

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

Effective date: 20230429

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

Ref country code: GB

Payment date: 20240404

Year of fee payment: 19

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

Ref country code: DE

Payment date: 20240403

Year of fee payment: 19

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

Ref country code: ES

Payment date: 20240607

Year of fee payment: 19

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

Ref country code: FR

Payment date: 20240408

Year of fee payment: 19

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

Ref country code: BE

Payment date: 20240422

Year of fee payment: 19