EP2531419B1 - Procede d'ouverture facile d'un opercule thermoscelle sur le buvant d'un recipient en verre et récipient correspondant - Google Patents
Procede d'ouverture facile d'un opercule thermoscelle sur le buvant d'un recipient en verre et récipient correspondant Download PDFInfo
- Publication number
- EP2531419B1 EP2531419B1 EP11705930.3A EP11705930A EP2531419B1 EP 2531419 B1 EP2531419 B1 EP 2531419B1 EP 11705930 A EP11705930 A EP 11705930A EP 2531419 B1 EP2531419 B1 EP 2531419B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heat
- glass jar
- seal
- equivalent container
- organic
- 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
Links
- 239000011521 glass Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000011888 foil Substances 0.000 title claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 31
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 12
- 239000012766 organic filler Substances 0.000 claims abstract description 11
- 239000011368 organic material Substances 0.000 claims abstract description 8
- 238000004806 packaging method and process Methods 0.000 claims abstract description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 5
- 239000011147 inorganic material Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 239000011256 inorganic filler Substances 0.000 claims abstract 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract 4
- 235000021067 refined food Nutrition 0.000 claims abstract 2
- 239000002987 primer (paints) Substances 0.000 claims description 27
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- -1 polypropylene Polymers 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920002530 polyetherether ketone Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 150000001735 carboxylic acids Chemical group 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000012764 mineral filler Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241001639412 Verres Species 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D77/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks or bags
- B65D77/10—Container closures formed after filling
- B65D77/20—Container closures formed after filling by applying separate lids or covers, i.e. flexible membrane or foil-like covers
- B65D77/2024—Container closures formed after filling by applying separate lids or covers, i.e. flexible membrane or foil-like covers the cover being welded or adhered to the container
- B65D77/2028—Means for opening the cover other than, or in addition to, a pull tab
- B65D77/2032—Means for opening the cover other than, or in addition to, a pull tab by peeling or tearing the cover from the container
Definitions
- the present invention relates to glass packaging (jar, bottle with wide opening, bottle, carafe, ...) having a rim forming a surface of any geometry (annular, oval, substantially rectangular or other) and on which is heat sealed a metal seal providing a tight seal.
- the rim is initially coated with a layer of heat-sealing primer, while the seal includes a layer of thermoplastic resin which allows heat-sealing by application of a sufficient temperature and pressure.
- the inventors therefore had the objective of solving these problems.
- the invention relates to a method of opening a lid comprising a metal sheet and a thermoplastic resin layer through which the lid is heat-sealed on the rim of a pot or equivalent container of glass, having previously coated with a heat-sealing primer, the heat-sealed lid providing a tight closure of the pot or equivalent container of glass; this process is distinguished by the fact that the initial and final tearing forces are at most 30 N, when the lid is peeled at 90 ° at a speed of 300 mm / min, and that the primer heat-sealing comprises an organic and / or inorganic material in which mineral and / or organic fillers are incorporated.
- the opening of the package is easy even for a relatively small person, and avoids tearing the lid in several pieces during peeling. This easy opening is now achieved while meeting the sustainable sealing requirements required for all content, including food.
- the subject of the invention is also an equivalent pot or container (bottle, flask, carafe, etc.) of glass suitable for carrying out the method described above, characterized in that the heat-sealing primer coating comprises a material organic and / or mineral in which are incorporated mineral and / or organic fillers.
- said organic material is the drying product of an aqueous dispersion of ethylene-acrylic acid copolymer whose carboxylic acid functions are partially or completely neutralized.
- This organic material may be alone or associated with at least one other organic and / or inorganic material - in addition to fillers - in the heat-sealing primer.
- This copolymer is solid and stable in its suspension at room temperature; the implementation by aqueous route is advantageous.
- the pot coated with heat-sealing primer thus obtained can be delivered to its user-filler without delay, which eliminates the need to store more or less large volumes of pots before delivery.
- the heat-sealing primer can contain mineral or organic fillers of one or more chemical natures, only mineral or organic fillers or both.
- said mineral fillers are incorporated in the dispersions of heat-sealing primer in the form of aggregates or powder of solid particles of sizes of between 1 nm and 20 ⁇ m, preferably between 150 nm and 10 ⁇ m, of one or more materials. selected from clays, kaolin, mica, talc, silicas, carbonates or alkaline earth sulfates, metal oxides.
- organic fillers When organic fillers are employed, they are advantageously of a different chemical nature from that of the heat-sealing primer (that is to say of the material constituting it excluding the fillers) as well as the thermoplastic resin of the cap, have a melting point higher than that of these two constituents and consist of particles of sizes of between 1 nm and 20 ⁇ m, preferably between 150 nm and 10 ⁇ m.
- Said organic fillers preferably comprise one or more polymers assembled in the form of copolymer, graft polymer, alloy or core-shell structure chosen from high density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), polyamide (PA), polyester, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), poly (ethylene glycol) (PEG), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polyetheretherketone (PEEK).
- HDPE high density polyethylene
- PP polypropylene
- PS polystyrene
- PA polyamide
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- PEG poly (ethylene glycol)
- PET polyethylene terephthalate
- PMMA polymethyl methacrylate
- PEEK polyetheretherketone
- Another object of the invention lies in the application of a method, or a pot or glass equivalent container described above, to the packaging of agri-food products, such as dairy or fruit-based, meat ( dough).
- agri-food products such as dairy or fruit-based, meat ( dough).
- the invention makes it possible to guarantee the preservation of the contents while respecting the conditions in particular of temperature prescribed for this purpose, and the tightness of the packaging in such conditions of conservation of the contents.
- a heat-sealing primer coating is deposited on the rim of the pot. Any other contact method, such as tempered, brush, buffer ... or without contact such as projection, spraying ... can be used.
- Heat sealing the primary is organic and comprises an aqueous dispersion of random linear copolymer ethylene-acrylic acid of average molecular weight M w of about 33 000 g / mol expressed in polystyrene equivalent.
- the copolymer comprises 9.1% of acrylic acid units and 90.9% of ethylene units.
- the carboxylic acid functions of the poly (ethylene-carboxylic acid) ionomer are neutralized to 100% with ammonia.
- the pH of the suspension is adjusted to between 8.5 and 9. According to the application method used, the solids content of the heat-sealing primer used varies from 0.2 to 10% by weight; it is here 9.5% in mass.
- This material has a broad melting peak between 70 and 95 ° C (Differential Scanning Calorimetry - DSC - 15 ° C / min).
- the heat sealing surface of the glass jar is roll coated with a uniform layer of primer having a mean dry thickness of 1.8 ⁇ m.
- the heat sealing is carried out according to standard settings applied in industrial conditions, by means of a soft-head heat sealer delivering a thrust of approximately 1560 N.
- the head is heated to 250 ° C, so that the temperature at the interface pot / lid reaches 149 to 155 ° C for a duration of application of pressure by the heated head of 1.5 s.
- the assembled system is waterproof.
- the peel forces are peeled at 90 ° C at a speed of 300 mm / min.
- the typical known pattern of peeling on this type of system can be described in three forces: the initial tearing force (AI), the flow force (FE) and the final tearing force (AF).
- the average of AI and AF is 44.8 N.
- the peeling of the operculum is therefore relatively difficult.
- Example 1 is reproduced except that the heat-sealing primer is mixed with a suspension of Na + partition previously dispersed with the deflocculator in deionized water at a speed of between 500 and 1000 revolutions / min. 10 minutes.
- the solids in the mixture obtained are 9.5% by weight of primer and 0.6% by mass of Na + partition.
- a homogeneous layer having a mean dry thickness of 1.8 ⁇ m is rolled.
- the mean of AI and AF is 18.9 N, corresponding to a relatively easy operculum peel, the addition of Na + partitioning making it possible to reduce by more than 50% the force required for this purpose (to be compared with that of Comparative Example 1).
- the operculum does not tear on peeling, after which no residue of thermoplastic resin originating from the lid is observed on the rim of the pot.
- the opening of the packaging can therefore be described as clean.
- Example 1 is reproduced with the difference that the heat-sealing primer is mixed with magnetic stirring to an aqueous suspension at pH 8.5. of polytetrafluoroethylene (PTFE) whose particles have an average size of 155 nm and containing a surfactant which does not interfere with the adhesion to the glass.
- PTFE polytetrafluoroethylene
- the solids in the mixture obtained are 9.5% by weight of primer and 4.5% by weight of PTFE.
- the average of AI and AF is 25.3 N, corresponding to a relatively easy operculum peel, the addition of PTFE making it possible to reduce by more than 40% the force required for this purpose.
- Example 1 is repeated with the difference that the thermosmoothing primer is mixed with magnetic stirring suspensions of Na + and PTFE partitions of Examples 2 and 3.
- the solids in the resulting mixture are adjusted to 9.5 % by weight of primer, 0.38% by mass of Na + partition and 3% by weight of PTFE.
- the formulation is deposited according to the same process and the same thickness as the previous examples.
- the mean of AI and AF is 14.8 N, corresponding to a very easy operculum peel, the joint addition of Na + and PTFE partitioning having allowed to reduce by more than 65% the force required for this purpose .
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Closures For Containers (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Closing Of Containers (AREA)
- Package Closures (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Glass Compositions (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1050738A FR2955844B1 (fr) | 2010-02-03 | 2010-02-03 | Procede d'ouverture facile d'un opercule thermoscelle sur le buvant d'un recipient en verre |
| PCT/FR2011/050148 WO2011095726A1 (fr) | 2010-02-03 | 2011-01-26 | Procede d'ouverture facile d'un opercule thermoscelle sur le buvant d'un recipient en verre et recipient correspondant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2531419A1 EP2531419A1 (fr) | 2012-12-12 |
| EP2531419B1 true EP2531419B1 (fr) | 2013-11-20 |
Family
ID=42557442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP11705930.3A Active EP2531419B1 (fr) | 2010-02-03 | 2011-01-26 | Procede d'ouverture facile d'un opercule thermoscelle sur le buvant d'un recipient en verre et récipient correspondant |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US9302837B2 (pt) |
| EP (1) | EP2531419B1 (pt) |
| AR (1) | AR080053A1 (pt) |
| BR (1) | BR112012019415B1 (pt) |
| CL (1) | CL2012002176A1 (pt) |
| ES (1) | ES2441812T3 (pt) |
| FR (1) | FR2955844B1 (pt) |
| PT (1) | PT2531419E (pt) |
| RU (1) | RU2566311C2 (pt) |
| UA (1) | UA106648C2 (pt) |
| WO (1) | WO2011095726A1 (pt) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HUE045436T2 (hu) | 2015-03-04 | 2019-12-30 | Cie Generale De Conserve | Hajlékony fenekû konzervdoboz és megfelelõ gyártási eljárás |
| FR3101861B1 (fr) | 2019-10-14 | 2021-11-12 | Groupe Daucy | Méthode de fabrication d’une boîte de conserve |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3748816A (en) * | 1969-10-02 | 1973-07-31 | R Asmus | Method of sealing a container |
| US4180961A (en) * | 1976-12-08 | 1980-01-01 | Aluminum Company Of America | Induction heat sealed containers |
| JPS5820604A (ja) * | 1981-07-20 | 1983-02-07 | 株式会社細川洋行 | ガラス容器の蓋材シ−ル方法 |
| US4396655A (en) * | 1982-03-08 | 1983-08-02 | Owens-Illinois, Inc. | Method of sealing a glass container with a thin membrane closure |
| US4913307A (en) * | 1986-09-30 | 1990-04-03 | Idemitsu Petrochemical Co., Ltd. | Easily openable packaging container and method for producing the same |
| US4771903A (en) * | 1986-11-14 | 1988-09-20 | Leon Levene | Glass container sealing method |
| NZ226028A (en) * | 1987-09-09 | 1990-06-26 | Idemitsu Petrochemical Co | Hermetically sealed package which can be resealed after opening |
| GB8729725D0 (en) * | 1987-12-21 | 1988-02-03 | Metal Box Plc | Container with peelable seal & method & apparatus for making same |
| US5062569A (en) * | 1988-08-01 | 1991-11-05 | Hekal Ihal M | Peelably sealed plastic packages and method of preparing same |
| US5004110A (en) * | 1989-08-03 | 1991-04-02 | Abbott Laboratories | Retortable closure for plastic container |
| US5160391A (en) * | 1991-04-15 | 1992-11-03 | James River Ii, Inc. | Method for the formation of a clamped wave seal structure |
| US7364779B2 (en) * | 2003-09-02 | 2008-04-29 | Sonoco Development, Inc. | Easy-opening high barrier plastic closure and method therefor |
| DE102004032100B4 (de) * | 2004-07-01 | 2006-06-22 | Rainer Ammann | Verfahren zum Ablösen bzw. Abtrennen einer auf den Rand des Halses einer Flasche od. dergl. aufgesiegelten Siegelfolie und Schraubkappen zur Ausführung dieser Verfahren |
| FR2889506B1 (fr) * | 2005-08-03 | 2010-08-27 | Flackpull | Ampoule operculee destinee a etre remplie d'un liquide par depression et procede de fabrication correspondant |
| GB0708692D0 (en) * | 2007-05-04 | 2007-06-13 | Innovia Films Ltd | Seelable, pealable film |
| ES2334275T3 (es) * | 2007-06-22 | 2010-03-08 | Selig Sealing Products, Inc. | Junta para un contenedor. |
| RU2490193C2 (ru) * | 2009-03-16 | 2013-08-20 | 1/4 Вэн | Стакан для вина, способ упаковывания вина и контейнер для вина |
| US20110017772A1 (en) * | 2009-07-24 | 2011-01-27 | Alcan Packaging Beauty Services | Container and Sealing Membrane for Packaging of Reactive Products |
| ES2739703T3 (es) * | 2010-02-26 | 2020-02-03 | Intercontinental Great Brands Llc | Envase que tiene un fijador de cierre reutilizable adhesivo y métodos para este |
| GB201107766D0 (en) * | 2011-05-10 | 2011-06-22 | Selig Sealing Products Inc | Coloured tabbed container closure liners |
| US20140166682A1 (en) * | 2012-12-19 | 2014-06-19 | Sonoco Development, Inc. | Container and Closure Assembly |
-
2010
- 2010-02-03 FR FR1050738A patent/FR2955844B1/fr active Active
-
2011
- 2011-01-26 WO PCT/FR2011/050148 patent/WO2011095726A1/fr active Application Filing
- 2011-01-26 BR BR112012019415A patent/BR112012019415B1/pt active IP Right Grant
- 2011-01-26 PT PT117059303T patent/PT2531419E/pt unknown
- 2011-01-26 EP EP11705930.3A patent/EP2531419B1/fr active Active
- 2011-01-26 RU RU2012137208/12A patent/RU2566311C2/ru active
- 2011-01-26 UA UAA201210288A patent/UA106648C2/uk unknown
- 2011-01-26 US US13/577,086 patent/US9302837B2/en active Active
- 2011-01-26 ES ES11705930.3T patent/ES2441812T3/es active Active
- 2011-01-28 AR ARP110100291A patent/AR080053A1/es active IP Right Grant
-
2012
- 2012-08-03 CL CL2012002176A patent/CL2012002176A1/es unknown
Also Published As
| Publication number | Publication date |
|---|---|
| RU2012137208A (ru) | 2014-03-10 |
| EP2531419A1 (fr) | 2012-12-12 |
| PT2531419E (pt) | 2014-01-29 |
| US9302837B2 (en) | 2016-04-05 |
| BR112012019415A2 (pt) | 2016-05-03 |
| UA106648C2 (uk) | 2014-09-25 |
| CL2012002176A1 (es) | 2013-07-12 |
| AR080053A1 (es) | 2012-03-07 |
| FR2955844A1 (fr) | 2011-08-05 |
| ES2441812T3 (es) | 2014-02-06 |
| WO2011095726A1 (fr) | 2011-08-11 |
| US20130036715A1 (en) | 2013-02-14 |
| RU2566311C2 (ru) | 2015-10-20 |
| BR112012019415B1 (pt) | 2020-04-22 |
| FR2955844B1 (fr) | 2012-04-27 |
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