EP1765513B1 - Recipient pour le conditionnement d'un liquide a distribuer goutte a goutte, a deformation reversible par admission d'air - Google Patents

Recipient pour le conditionnement d'un liquide a distribuer goutte a goutte, a deformation reversible par admission d'air Download PDF

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Publication number
EP1765513B1
EP1765513B1 EP05756044.3A EP05756044A EP1765513B1 EP 1765513 B1 EP1765513 B1 EP 1765513B1 EP 05756044 A EP05756044 A EP 05756044A EP 1765513 B1 EP1765513 B1 EP 1765513B1
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EP
European Patent Office
Prior art keywords
container
liquid
drop
packaging
dispensed
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
EP05756044.3A
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German (de)
English (en)
French (fr)
Other versions
EP1765513A1 (fr
Inventor
Michel Faurie
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.)
Laboratoires Thea SAS
Original Assignee
Laboratoires Thea SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Laboratoires Thea SAS filed Critical Laboratoires Thea SAS
Priority to DK18183420.1T priority Critical patent/DK3412590T3/da
Priority to PL18183420T priority patent/PL3412590T3/pl
Priority to SI200532232T priority patent/SI1765513T1/sl
Priority to EP18183420.1A priority patent/EP3412590B1/fr
Priority to PL05756044T priority patent/PL1765513T3/pl
Publication of EP1765513A1 publication Critical patent/EP1765513A1/fr
Application granted granted Critical
Publication of EP1765513B1 publication Critical patent/EP1765513B1/fr
Priority to CY20211100912T priority patent/CY1124636T1/el
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • B65D47/00—Closures with filling and discharging, or with discharging, devices
    • B65D47/04—Closures with discharging devices other than pumps
    • B65D47/06—Closures with discharging devices other than pumps with pouring spouts or tubes; with discharge nozzles or passages
    • B65D47/18—Closures with discharging devices other than pumps with pouring spouts or tubes; with discharge nozzles or passages for discharging drops; Droppers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
    • B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
    • B05B11/04—Deformable containers producing the flow, e.g. squeeze bottles
    • 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
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/32—Containers adapted to be temporarily deformed by external pressure to expel contents

Definitions

  • the invention is in the field of packaging and dispensing liquids, such as pharmaceutical solutions and especially eye drops. It relates to a container equipped with a dispensing head, which is organized to contain a liquid by protecting it from the outside environment and to deliver this liquid in a controlled manner, particularly drop by drop.
  • Containers for containing a liquid which are organized to preserve this liquid from the outside environment and to deliver it in a controlled manner, in particular drop by drop.
  • the applications of such containers are numerous, and a preferred application, but not restrictive as to the scope of the present invention, lies in the preservation and distribution of a pharmaceutical solution, especially eye drops.
  • the preservation of the liquid With regard to the preservation of the liquid, it must be protected from the outside environment by avoiding contact with the ambient air which is likely to contain pollutants, including bacteria.
  • the container For the distribution of the liquid, it is common to give the container a deformable character to reduce its capacity, at least temporarily, to evacuate the liquid it contains.
  • Such containers are more precisely flexible wall, to cause evacuation of the liquid from a compression exerted by the user on this wall, and they are equipped with a dispensing head, to achieve the two objectives that are the preservation and controlled distribution of the liquid.
  • a first approach it has been proposed to give the container an irreversible or almost irreversible deformable character.
  • An inner wall of the container defining the liquid receiving capacity is organized bellows, and is wrapped with an outer sheath.
  • This container further contains a filter membrane which has a character impervious to air, to prohibit an intake of outside air to the liquid in the container, under the effect of a withdrawal of liquid delivered.
  • patent documents may be referred to FR 2 661 401 and FR 2,770,495 (or US6,336,571 ), which describe such containers.
  • a microporous buffer acting as a flow regulator is disposed in the dispensing head of a rigidly irreversible deformation wall container.
  • An intermediate reserve is provided downstream of the buffer and upstream of an impervious membrane filter.
  • Such a container has a complex structure, and the manufacturing cost of both the reservoir for containing the liquid to be dispensed and the dispensing head is high.
  • the dispensing head of this container is simple. It contains a filter membrane that aims to preserve the liquid pollutants that may be present in the ambient air. It is further planned to preserve the liquid rigorously ambient environment before first use.
  • the dispensing head is movably mounted on the neck of the container, for the perforation of a cap extemporaneously to a first delivery operation.
  • the present invention is part of this search for compromise, and aims to provide a container for the packaging of a liquid to be dispensed drop by drop which offers a solution to such a compromise.
  • the invention more specifically relates to the packaging of a sensitive liquid, such as a pharmaceutical, biological or similar solution, especially eye drops.
  • the inventive step of the present invention consisted in its generality, to first choose a container of the type comprising a wall tank with elastically reversible deformation by admission of air inside the container.
  • This choice is intended to allow a delivery of the liquid under the effect of a pressure exerted against this wall, and to allow a spontaneous return of the container to its initial conformation after delivery of a dose of liquid.
  • a wall tank with reversible deformation already has in itself the advantage of great simplicity of manufacture, compared to irreversible deformation tanks of the prior art, which require a number of parts and operations of important assembly.
  • such a container will be recognized according to the present invention in that it is equipped with a dispensing head comprising a hollow body which is provided with a nozzle for delivering the liquid and which contains a microporous pad of hydrophobic material. placed downstream of the tank across the body of the dispensing head. Said body is irreversibly assembled inside the neck of the container.
  • the passage of air is authorized by suction through the hydrophobic microporous pad to the storage capacity after delivery of a dose of liquid, this suction being caused by the elastic return of the vessel wall to its initial conformation , return by which the container returns to its original shape notwithstanding a withdrawal of a dose of liquid.
  • microporous pad is preferably made of polyethylene, or similar material, which gives it a hydrophobic character so that it is not wettable, its microporous nature nevertheless allowing the passage of the liquid through it provided that the differential of pressure, induced by the pressure exerted by the user, is sufficient.
  • Such a configuration of the container according to the invention, and more particularly the combination between the reversible deformation reservoir, the microporous pad and the sealing cap, is quite advantageous. Indeed, when the cap is returned to the sealed sealing position of the nozzle, after the air suction following the delivery of a dose of liquid and the elastic return of the container wall to its initial conformation, it a pressure difference is created between the parts upstream and downstream of the buffer through which a pressure drop is created. This pressure difference prevents the liquid contained in the container from passing through the buffer, even if it is accidentally pressed on the wall of the container, and it seals the bottle, while protecting the liquid contained therein from external contaminations . In addition, such a configuration avoids stagnation of liquid downstream of the buffer, since the non-expelled liquid is sucked back to the capacity of the container.
  • the container according to the invention advantageously meets an objective of the invention, which is to ensure optimum use of the entire contents of the tank, and this in two different ways.
  • the container thanks to its elastically reversible deformation wall, the container retains a capacity to expel the intact liquid to the last drop of liquid. Indeed, because air is sucked into the container to replace each dose of liquid expelled, the expulsion pressure available in the bottle is always the same throughout the use, and until the distribution of the last drop.
  • there is no downstream of the buffer any drop of liquid likely to be contaminated by external agents, and should be eliminated before any new distribution of a clean dose.
  • the microporous buffer plays a role of flow regulator, which promotes the controlled distribution of liquid doses.
  • it prevents the liquid contained in the bottle from flowing when the cap is removed, even when the bottle is in the inverted position, the dispensing head being directed downwards, as long as no pressure is exerted on the wall of the container.
  • the dispensing head is preferably equipped with a filtering membrane intended to protect the liquid from an intake of pollutants present in the ambient air, bacteria especially.
  • a membrane that is at least partly hydrophilic and at least partly hydrophobic is then chosen, to alternatively allow the passage of liquid and air through it, and which is disposed in the dispensing head in upstream of the nozzle, between it and the buffer.
  • the partially hydrophilic nature of the membrane allows the liquid to pass therethrough under the effect of the compression exerted in the container by deformation of the wall, whereas its partially hydrophobic nature allows an entry of the outside air into the container. when the latter elastically resumes its initial shape after each compression exerted by the user.
  • the membrane furthermore advantageously constitutes an additional pressure drop, which ensures, in combination with the hydrophobic microporous pad, that no leakage of liquid from the container occurs until the wall of the container is compressed.
  • the invention In order to promote the passage of air through the membrane, the invention then provides that it is possible to maintain this dry membrane between two liquid deliveries, when the container is in a rested position on its base, thanks to the presence an intermediate chamber arranged in interposition between the microporous pad and the membrane.
  • Such an intermediate chamber can also be used to constitute a regulation chamber of the delivery of the liquid.
  • the volume of the intermediate chamber is also advantageously an air reserve which, when the nozzle is closed by the cap, retains a pressure which tends to prevent the liquid from passing through the microporous pad. It will be noted that, in combination with the intermediate chamber, the hydrophobic nature of the microporous buffer promotes an obstacle preventing the passage of the liquid through it.
  • the intermediate chamber is also advantageously a capacity to accommodate the liquid that has not yet passed through the membrane when it ceases to exert pressure on the wall of the container. For this, it is advantageous to ensure that the intermediate chamber extends over the entire surface of the membrane and that it is located at an axial distance from it sufficient to promote the drying of the membrane when the pressure exerted on the wall of the container ceases after delivery of liquid, and that the container is returned to its rest position, resting on its base and the dispensing head at the top. As a result, any residue of liquid which, having not been expelled, remains contained in the intermediate chamber, does not persist in wetting the membrane by capillarity. It will be noted that the hydrophobic nature of the microporous buffer also promotes the drying of the membrane.
  • the invention has the advantage, in industrial practice, to overcome the complex systems of dynamic closure that was used previously. Thanks to the provisions of the invention, there is no need for a lid or other tear-off partition, or a valve of other shape, or a procedure for opening the bottle by translation or rotation of the dispensing head with respect to the liquid reservoir container to be dispensed drip.
  • a microporous pad quite suitable for the purposes of the invention has, for the passage of the liquid in the longitudinal direction, microchannels whose average pore diameter is between 0.3 and 10 microns.
  • Such a range of values is particularly particularly suitable in the preferred field of application of the invention, which is the storage and distribution of a pharmaceutical solution, especially eye drops.
  • microporous buffer with a partially hydrophilic and partially hydrophobic membrane whose pore diameter is smaller than that of the buffer, in particular between 0.1 and 0.2 microns.
  • a partially hydrophilic and partially hydrophobic membrane whose pore diameter is smaller than that of the buffer, in particular between 0.1 and 0.2 microns.
  • the membrane may be made of a polymeric material, based for example on polyamide resin or polyether sulfone, which gives it a hydrophilic character. It is then rendered partially hydrophobic by modifying its structure on part of its surface. Such a modification can be carried out in a conventional manner in itself, for example by grafting in the presence of an initiator of radical reactions. The treatment is advantageously carried out so as to render the membrane hydrophobic on a median strip occupying 20 to 50% of its surface which is wetted during the expulsion of the liquid.
  • the body is assembled inside the neck by interlocking in close contact.
  • the body is preferably elastically deformable for its introduction into force inside the neck of the container, a centering member being preferably formed at the base of the body to facilitate such a force introduction.
  • This centering member is preferably constituted by radial junction wings by interlocking the body of the dispensing head on the neck of the container, the flanges delimiting between them recessed areas.
  • the outer surface of the body of the dispensing head is advantageously equipped with a peripheral ring from said body with which it constitutes a unitary assembly, this ring being preferably in plurality and axially repeated on the body.
  • the body is advantageously obtained by molding, under conditions such that a rod, issuing from the joint plane, is radial to its general axis of extension, and in particular if appropriate parallel to the aforementioned peripheral ring.
  • This ring resulting from the joint plane is more particularly located at the distal end of the body, at the junction limit of the centering member, to promote the best seal between the dispensing head and the container.
  • the removable cap meanwhile is preferentially reported on the container by screwing to promote the clamping of the cap on the dispensing head, and therefore the seal between these bodies.
  • the cap advantageously comprises a combination of sealing members associating a picot penetrating inside the nozzle of the dispensing head and a skirt covering this nozzle.
  • the pin and the skirt are advantageously derived from the cap, when obtaining the latter in one piece, particularly by molding.
  • a container for the conditioning of a liquid 1 is of spontaneously reversible deformation, to allow a distribution of the liquid 1 from a manual compression exerted by a user of its wall 2 and spontaneous return to its initial form by admission of 'air.
  • This container has a liquid storage capacity 1, and is equipped with a dispensing head 3 of the liquid drop by drop.
  • This dispensing head 3 consists mainly of a hollow body 4 provided with a nozzle 5, and a removable cap 6 for closing off the nozzle 5.
  • An antibacterial, partially hydrophilic and partially hydrophobic filter membrane 7, therefore permeable to air but also to the liquid, is disposed upstream of the nozzle 5, to protect the liquid against an unwanted introduction of pollutants possibly present in the ambient air, including bacteria.
  • the body 4 of the dispensing head 3 houses in its inner recess a microporous pad 8 which is made of a hydrophobic material, especially polyethylene, to prevent the passage of the liquid 1 to the nozzle 5, in the absence of compression on the wall 2 of the container.
  • This microporous buffer 8 is disposed upstream and away from the membrane 7, so as to provide between itself 8 and the latter 7 an intermediate chamber 9.
  • the chamber 9 extends over the entire surface of the pad so as to constitute a reserve of air which exerts, when the nozzle 5 is closed by the cap 6, a pressure on the entire surface of the pad 8 preventing the liquid 1 to pass through the microporous pad 8 when the nozzle 5 is closed by the cap 6. More specifically, the cap 6 prevents an evacuation of air out of the container, and more particularly out of the intermediate chamber 9. The air being confined downstream of the microporous pad 8, the latter obstructs the passage of the liquid 1 through it as long as the nozzle 5 is closed by the cap 6. Conversely for delivery of the liquid 1, the microporous pad 8 does not prevent this. delivery since the air can be discharged from the container through the nozzle 5.
  • the intermediate chamber 9 is used to allow a spontaneous regularization of the flow of the liquid 1 through the microporous buffer 8, preliminary its distribution through the nozzle 5.
  • the intermediate chamber 9 extends over the entire surface of the membrane so as to constitute a capacity to collect the liquid 1 away from the membrane 7 when it stops exerting pressure on the wall 2 of the container and thus to favor the drying of the membrane between two liquid deliveries.
  • the body 4 is assembled permanently inside the neck 10 of the container, by interlocking force. According to the various variants illustrated on the figure 1 and the figure 2 this interlocking is achieved either directly by close contact between the outer surfaces of the body 4 and the inside of the neck 10, as illustrated in FIG. figure 1 , and preferably via O-rings 11 formed at the periphery of the body 4, as illustrated in FIG. figure 2 .
  • a centering member 12 formed at the base of the body 4 to facilitate its introduction into the neck 10 of the container.
  • the centering element 12 illustrated for example is generally constituted radial junction wings 13 by interlocking the body 4 on the neck 10, the wings 13 delimiting between them recessed areas, more particularly visible on the figure 3 .
  • the variants shown illustrate the assembly by screwing the cap 6 on the neck 10 of the container, through cooperating reliefs 14.
  • the cap 6 comprises a pin 15 penetrating inside the nozzle 5 of the dispensing head and a skirt 16 styling the nozzle.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Closures For Containers (AREA)
  • Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
EP05756044.3A 2004-06-24 2005-06-24 Recipient pour le conditionnement d'un liquide a distribuer goutte a goutte, a deformation reversible par admission d'air Active EP1765513B1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DK18183420.1T DK3412590T3 (da) 2004-06-24 2005-06-24 Via lufttilførsel reversibelt deformeret beholder til pakning af en væske, der skal dispenseres i dråber
PL18183420T PL3412590T3 (pl) 2004-06-24 2005-06-24 Pojemnik do pakowania cieczy do dozownika, dozującego kropla po kropli, odkształcalny odwracalnie w wyniku dopływu powietrza
SI200532232T SI1765513T1 (sl) 2004-06-24 2005-06-24 Vsebnik za shranjevanje tekočine za odmerjanje v kapljicah, reverzibilno deformiranih z dovajanjem zraka
EP18183420.1A EP3412590B1 (fr) 2004-06-24 2005-06-24 Récipient pour le conditionnement d'un liquide à distributeur goutte à goutte, à déformation réversible par admission d'air
PL05756044T PL1765513T3 (pl) 2004-06-24 2005-06-24 Pojemnik do pakowania cieczy przeznaczonej do dozowania w kroplach odkształcany odwrotnie poprzez wprowadzenie powietrza
CY20211100912T CY1124636T1 (el) 2004-06-24 2021-10-20 Περιεκτης για τη συσκευασια ενος υγρου που χορηγειται σε σταγονες αντιστροφα παραμορφωμενος δια εισαγωγης αερα

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0407042A FR2872137B1 (fr) 2004-06-24 2004-06-24 Recipient pour le conditionnement d'un liquide a distributeur goutte a goutte, a deformation reversible par admission d'air
PCT/IB2005/001791 WO2006000897A1 (fr) 2004-06-24 2005-06-24 Recipient pour le conditionnement d’un liquide a distribuer goutte a goutte, a deformation reversible par admission d’air

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP18183420.1A Division EP3412590B1 (fr) 2004-06-24 2005-06-24 Récipient pour le conditionnement d'un liquide à distributeur goutte à goutte, à déformation réversible par admission d'air
EP18183420.1A Division-Into EP3412590B1 (fr) 2004-06-24 2005-06-24 Récipient pour le conditionnement d'un liquide à distributeur goutte à goutte, à déformation réversible par admission d'air

Publications (2)

Publication Number Publication Date
EP1765513A1 EP1765513A1 (fr) 2007-03-28
EP1765513B1 true EP1765513B1 (fr) 2018-08-22

Family

ID=34949309

Family Applications (2)

Application Number Title Priority Date Filing Date
EP18183420.1A Active EP3412590B1 (fr) 2004-06-24 2005-06-24 Récipient pour le conditionnement d'un liquide à distributeur goutte à goutte, à déformation réversible par admission d'air
EP05756044.3A Active EP1765513B1 (fr) 2004-06-24 2005-06-24 Recipient pour le conditionnement d'un liquide a distribuer goutte a goutte, a deformation reversible par admission d'air

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP18183420.1A Active EP3412590B1 (fr) 2004-06-24 2005-06-24 Récipient pour le conditionnement d'un liquide à distributeur goutte à goutte, à déformation réversible par admission d'air

Country Status (27)

Country Link
US (1) US7971755B2 (lt)
EP (2) EP3412590B1 (lt)
JP (2) JP5080972B2 (lt)
KR (1) KR100919520B1 (lt)
CN (1) CN100475359C (lt)
AR (1) AR051064A1 (lt)
BR (1) BRPI0512387B8 (lt)
CA (1) CA2572048C (lt)
CY (2) CY1120837T1 (lt)
DK (2) DK3412590T3 (lt)
ES (2) ES2691721T3 (lt)
FR (1) FR2872137B1 (lt)
HK (1) HK1104253A1 (lt)
HU (2) HUE056784T2 (lt)
LT (2) LT3412590T (lt)
MA (1) MA28671B1 (lt)
MX (1) MXPA06014657A (lt)
MY (1) MY164320A (lt)
NO (1) NO343517B1 (lt)
PL (2) PL1765513T3 (lt)
PT (2) PT1765513T (lt)
RU (1) RU2385774C2 (lt)
SI (2) SI1765513T1 (lt)
TN (1) TNSN06415A1 (lt)
TR (1) TR201815132T4 (lt)
WO (1) WO2006000897A1 (lt)
ZA (1) ZA200700248B (lt)

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JP2008503410A (ja) 2008-02-07
CY1124636T1 (el) 2022-07-22
FR2872137B1 (fr) 2009-01-23
MXPA06014657A (es) 2007-02-12
RU2385774C2 (ru) 2010-04-10
AR051064A1 (es) 2006-12-20
NO343517B1 (no) 2019-04-01
TR201815132T4 (tr) 2018-11-21
NO20070474L (no) 2007-03-26
US7971755B2 (en) 2011-07-05
KR20070027738A (ko) 2007-03-09
BRPI0512387A (pt) 2008-03-11
JP5080972B2 (ja) 2012-11-21
CY1120837T1 (el) 2019-12-11
JP2012210979A (ja) 2012-11-01
DK1765513T3 (en) 2018-11-26
PL3412590T3 (pl) 2022-01-24
BRPI0512387B1 (pt) 2018-11-06
EP1765513A1 (fr) 2007-03-28
TNSN06415A1 (fr) 2008-02-22
ZA200700248B (en) 2008-05-28
FR2872137A1 (fr) 2005-12-30
HUE039799T2 (hu) 2019-02-28
JP5307916B2 (ja) 2013-10-02
MY164320A (en) 2017-12-15
ES2691721T3 (es) 2018-11-28
BRPI0512387B8 (pt) 2019-01-15
ES2891874T3 (es) 2022-01-31
LT1765513T (lt) 2018-11-12
CA2572048A1 (fr) 2006-01-05
EP3412590A1 (fr) 2018-12-12
HK1104253A1 (en) 2008-01-11
CN1972755A (zh) 2007-05-30
WO2006000897A1 (fr) 2006-01-05
DK3412590T3 (da) 2021-10-11
MA28671B1 (fr) 2007-06-01
US20080067194A1 (en) 2008-03-20
PT1765513T (pt) 2018-11-20
RU2007101567A (ru) 2008-07-27
PL1765513T3 (pl) 2019-01-31
LT3412590T (lt) 2021-11-10
CN100475359C (zh) 2009-04-08
SI3412590T1 (sl) 2022-01-31
HUE056784T2 (hu) 2022-03-28
PT3412590T (pt) 2021-09-29
SI1765513T1 (sl) 2018-12-31
EP3412590B1 (fr) 2021-08-04
KR100919520B1 (ko) 2009-09-28

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