EP2591196B1 - Tür oder Fenster mit geschäumtem Einsatz, Herstellungsverfahren eines Tür- oder Fensterprofils mit solchem Schaum, und Teilesatz mit Tür- oder Fensterrahmenprofil und geschäumten Einsatz. - Google Patents

Tür oder Fenster mit geschäumtem Einsatz, Herstellungsverfahren eines Tür- oder Fensterprofils mit solchem Schaum, und Teilesatz mit Tür- oder Fensterrahmenprofil und geschäumten Einsatz. Download PDF

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Publication number
EP2591196B1
EP2591196B1 EP11729423.1A EP11729423A EP2591196B1 EP 2591196 B1 EP2591196 B1 EP 2591196B1 EP 11729423 A EP11729423 A EP 11729423A EP 2591196 B1 EP2591196 B1 EP 2591196B1
Authority
EP
European Patent Office
Prior art keywords
foam
door
profile
window
compressed
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.)
Not-in-force
Application number
EP11729423.1A
Other languages
English (en)
French (fr)
Other versions
EP2591196A1 (de
Inventor
Koen Vanlandschoot
Peter Spanhove
Laura Jonckheere
Mario Genetello
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.)
Recticel NV SA
Original Assignee
Recticel NV SA
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
Priority claimed from EP10168485A external-priority patent/EP2405092A1/de
Application filed by Recticel NV SA filed Critical Recticel NV SA
Priority to EP11729423.1A priority Critical patent/EP2591196B1/de
Publication of EP2591196A1 publication Critical patent/EP2591196A1/de
Application granted granted Critical
Publication of EP2591196B1 publication Critical patent/EP2591196B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/04—Wing frames not characterised by the manner of movement
    • E06B3/263—Frames with special provision for insulation
    • E06B3/277—Frames with special provision for insulation with prefabricated insulating elements held in position by expansion of the extremities of the insulating elements
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/04—Wing frames not characterised by the manner of movement
    • E06B3/263—Frames with special provision for insulation
    • E06B3/2632—Frames with special provision for insulation with arrangements reducing the heat transmission, other than an interruption in a metal section
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/04—Wing frames not characterised by the manner of movement
    • E06B3/263—Frames with special provision for insulation
    • E06B3/2632—Frames with special provision for insulation with arrangements reducing the heat transmission, other than an interruption in a metal section
    • E06B2003/26321—Frames with special provision for insulation with arrangements reducing the heat transmission, other than an interruption in a metal section with additional prefab insulating materials in the hollow space
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/04—Wing frames not characterised by the manner of movement
    • E06B3/263—Frames with special provision for insulation
    • E06B2003/26349—Details of insulating strips
    • E06B2003/26369—Specific material characteristics
    • E06B2003/26378—Specific material characteristics comprising foam

Definitions

  • the present invention concerns a door or window comprising a frame profile comprising a foamed insert.
  • Window frames and door frames are known to be manufactured in aluminum or PVC or wood.
  • Aluminum frames generally comprise profiles with an inner and an outer shell coupled by a thermal bridge.
  • This thermal bridge is known to comprise a structure in a non-thermal conductive material such as polyamide, extending between the inner shell and outer shell, thereby defining one or several inner chambers.
  • This thermal bridge does not or only on a very limited scale provide structural strength to the profile and should be kept as small as possible to ensure structural integrity of the profile as such.
  • the structural strength of the profile is key to minimizing width of the frame for supporting a glass panel or such.
  • DE 3 440 710 shows a PUR-insert that swells when heated.
  • EP 2,080,864 discloses an insert for frame profiles comprising a thermal insulating foam and a structural strengthening band embedded therein.
  • An inconvenience of this type of insert is that it is rather difficult to insert it into the inner chamber of a profile and in that it does not provide a support over the entire surface of the inner chamber wherein the insert is provided.
  • the present invention meets this demand by providing a specific foamed insert for frame profiles.
  • the present invention concerns a door or window comprising a frame profile comprising a foamed insert, characterized in that said foam is shape memory polymer foam.
  • the present invention further concerns a kit of parts comprising a window or door frame profile having an inner chamber and a shape memory polymer foam strip, the foam having a Tg above room temperature (20°C).
  • the present invention concerns a method for manufacturing such a door or window frame profile.
  • the frame profile preferably comprises walls defining an inner chamber wherein said foam is inserted in its compressed state and wherein substantially the entire outer surface of the foam insert contacts the inner surface of said inner chamber upon foam expansion.
  • the foam used for the insert is preferably a polyurethane foam with a Tg (glass transition temperature) above room temperature, preferably between 20 and 120°C, more preferably between 30 and 70°C, even more preferably between 40 and 60°C and even more preferably between 50 and 55°C.
  • Tg glass transition temperature
  • the kit of parts wherein the foam strip is compressed to have a cross section dimension smaller than the cross section dimension of the inner chamber of the profile.
  • Figure 1 and Figure 2 represent a cross sectional perspective view of an aluminum type of frame profile 1 according to the present invention.
  • the profile comprises an inner shell 2 and an outer shell 3 that are connected to each other by a thermal bridge 4.
  • the thermal bridge comprises two legs 5, 6 each extending longitudinally and at a distance from each other between the inner shell 2 and the outer shell 3, thereby defining an inner chamber 7.
  • Figure 3 represents a PVC type frame profile according to the present invention, the profile comprising at least four longitudinally extending legs defining an inner chamber 8.
  • the inner chamber is provided with a foam insert 9 so that substantially the entire outer surface 9 of the foam insert contacts the inner surface of said inner chamber 7, 8.
  • the foam is a shape memory polymer foam, preferably a shape memory polyurethane (PU) foam.
  • Shape memory polymer foams are hereby defined as foams that remain compressed (or deformed) if they are compressed at a temperature higher than the glass transition temperature (Tg) of the polymer and then cooled below Tg in their compressed or deformed state. They substantially recover from their compressed state to their expanded state when heated to a temperature higher than Tg.
  • the expanded state is the shape of the shape memory material after it is manufactured and before it is compressed. The recovery of the foam to its expanded shape is referred to as "shape memory”.
  • the shape memory polymer foam of the present invention can be made from styrene-butadiene polymers, crystalline diene polymers, norbornane polymers, and the like. Most preferably, the shape memory polymer foam is a polyurethane foam or a poly-isocyanate based foam having a Tg which is above room temperature. The foam is rigid at room temperature and becomes elastic when it is heated above the Tg.
  • the properties, such as Tg, of the shape memory polyurethane foam are achieved by careful selection of the polyurethane foam forming components, such as the used polyisocyanate (not limited to TDI, MOI, NCO-terminated prepolymer), the used polyol (not limited to a polyether, polyester, polycarbonate, OH-terminated prepolymer), and the used chain extender.
  • the used polyisocyanate not limited to TDI, MOI, NCO-terminated prepolymer
  • the used polyol not limited to a polyether, polyester, polycarbonate, OH-terminated prepolymer
  • the used chain extender such as the used chain extender.
  • these properties can be tailored in such a way that even below Tg, i.e. in rigid state, the foam can be mechanically compressed up to 25 % without destructing the cellular foam structure and even fulfilling its shape memory function at temperatures above Tg.
  • the PU foam preferably has a Tg above room temperature and below the melting or deterioration temperature of the most heat sensitive material delimiting the chamber wherein the foam is inserted.
  • the Tg of the shape memory polymer foam is preferably not higher than the temperature to which the thermal bridge itself (i.e. in an non-assembled state with the outer and inner shells 2, 3) can be exposed without damaging it.
  • the Tg of the shape memory polymer foam is preferably below 55°C.
  • the shape memory polymer foam has a Tg higher than room temperature such that it can easily be stored and transported in a compressed form, without expanding.
  • a Tg of the shape memory polymer foam ranging between 20°C and 120°C, or better between 30 and 70°C, or even better between 40°C and 60°C is preferred.
  • Most preferred is a Tg ranging between 50°C and 55°C, in which case the shape memory polymer foam remains in its structurally more rigid condition at normal temperatures to which door- and window frames are exposed in normal use.
  • the shape memory polymer foam preferably has an open cell structure.
  • the open cell structure can be achieved in various ways, for example by appropriate selection of cell openers and/or surfactants, or by reticulation methods applied on foams in their elastic state (above Tg).
  • the open cell structure of the foam allows it to be compressed to a much larger degree. If the shape memory polymer foam is of closed cell structure, it recovers to its original shape rapidly upon expansion of the cell gas which has been compressed in the cells during compression.
  • the cells in the shape memory polymer foam should have a cell diameter in the range of between 100 ⁇ m and 800 ⁇ m or lower in order to obtain good thermal insulation properties.
  • the foam is further preferably a hydrophobic foam to prevent water absorption and loss of thermal insulation properties over an extended period of time.
  • the shape memory polymer foam may have a cellular or a micro-cellular structure, having a density (in expanded state) in the range of from 20 kg/m 3 and 800 kg/m 3 . Most preferably the shape memory polymer foam has a density between 25 kg/m 3 and 200 kg/m 3 , in view of the ease of compression.
  • the shape memory polymer foam is further characterized by a compression strength (hardness) of between 150 kPa and 300 kPa at 15 % compression and of between 170 and 370 kPa at 40 % compression, when measured with following test method.
  • a polymer foam sample with a dimension of 10 cm (length) * 10 cm (width) * 2 cm (height) is compressed (after 24 hours of conditioning at 23 ⁇ 2 °C and a relative humidity of 50 ⁇ 10 %) in the height direction at a rate of 120 mm/min.
  • the compression force at 15 % and at 40 % compression is then measured.
  • the foam preferably has a compression modulus of at least 500 kPa, preferably at least 1000 kPa, preferably at least 2000 kPa, more preferably at least 2500 kPa, most preferably at least 3000 kPa, while compression moduli up to 10000 kPa or more should not be excluded.
  • the bending strength of the shape memory foam preferably ranges between 25 and 500 kPa, when measured with following test method.
  • a polymer foam sample with a dimension of 12 cm (length) * 2 cm (width) * 1 cm (height) is (after 24 hours of conditioning at 23 ⁇ 2 °C and a relative humidity of 50 ⁇ 10 %) positioned on supports that are spaced apart at a distance of 10 cm.
  • the foam sample is bent at a constant rate of 50 mm/min.
  • the bending force is measured at sample fracture or at a maximum bending of 40 mm.
  • the bending modulus of the foam is preferably at least 500 kPa, preferably at least 750 kPa, more preferably at least 1000 kPa and can range upto 5000 kPa and even 9000 kPa or more.
  • the shape memory foam preferably has a fixity rate of at least 0,70, preferably at least 0,80, most preferably at least 0,90, wherein the fixity rate is measured by:
  • the fixity rate is than calculated by height of block at 25°C before release / height of block at 25 °C 30 minutes after release.
  • a frame profile according to the present invention can exhibit improved structural properties of the thermal bridge or parts of the profile due to the presence of the expanded shape memory polymer foam exerting an evenly divided pressure outwardly directed on the side walls of the inner chamber 7, 8.
  • the evenly divided pressure is preferably achieved by dimensioning the foam strip such that when allowed to fully expand to its original dimensions, it has a height or width or a height and width larger than the height and/or width of the inner chamber wherein it is inserted
  • the profile is assembled by inserting the foam, which will be typically in the form of a strip 10 of compressed shape memory polymer foam having cross sectional dimensions (height or width or both) smaller than the cross sectional dimensions (height or width or both) of the inner chamber, in that inner chamber 7, 8, such as represented in figure 2 .
  • Compression of the foam strip can be for example achieved on site by introducing an expanded foam strip between a pair of rolls (heated slightly above the Tg of the foam) and immediate insertion of the compressed strip in the profile.
  • the profile can be heated up to a temperature above the Tg of the shape memory polymer foam used, such that the foam strip will expand until it takes the shape of the inner chamber thereby contacting substantially the entire inner surface of said inner chamber 7, 8.
  • This method wherein the foam is expanded in the profile before sizing the profile, allows to obtain a good control on the use of the foam and especially to guarantee that the foam is applied over the entire length of the profile without interruption and to prevent that debris originating from further handling of the profile enters the inner chamber. In this way an optimal insulation of the frame by the foam is assured.
  • the foam strip can be inserted and expanded before the thermal bridge is connected to the inner and outer shells 2, 3 of the profile. Otherwise, it is also possible to insert the strip in the inner chamber of the profile or the thermal bridge, to size the profile and assemble the frame of a door or window, and to heat the sized profile or frame above Tg of the foam to expand said foam. In this case, heating of the frame can be combined with the production step of drying a lacquer or powder coating provided in the frame.
  • the foam strip will remain in place due to friction with the walls of the inner chamber and one can guarantee that substantially the entire inner chamber is filled with foam, thereby assuring thermal insulation, damping and sound insulation properties.
  • the present invention allows for providing alternative profile structures having different choice of selection of materials, wall thickness of the profiles and/or design of single or multiple chamber profile cross sections. Hence, efficient and cost effective optimization of profiles is obtained.

Claims (14)

  1. Tür oder Fenster bestehend aus einem Rahmenprofil, wobei das Profil (1) einen Schaumstoffeinsatz (9) umfasst, dadurch gekennzeichnet, dass es sich bei diesem Schaumstoff um einen Formgedächtnispolymerschaum handelt.
  2. Die Tür oder das Fenster gemäß Anspruch 1, wobei das Rahmenprofil Wände aufweist, die eine innere Kammer definieren (7, 8), worin dieser Schaumstoff eingesetzt wird und wo im Wesentlichen die gesamte Außenfläche des Schaumstoffeinsatzes (9) Kontakt mit der Innenfläche der inneren Kammer (7, 8) hat.
  3. Die Tür oder das Fenster gemäß Anspruch 1, wobei es sich beim dem Schaumstoff um einen Polyurethanschaum handelt.
  4. Die Tür oder das Fenster gemäß Anspruch 1, wobei der Schaumstoff eine Tg (Glastemperatur) über 20°C hat.
  5. Die Tür oder das Fenster gemäß Anspruch 4, wobei der Schaumstoff einen Tg-Bereich zwischen 30°C und 120°C, vorzugsweise zwischen 30°C und 70°C und besonders vorzugsweise zwischen 40°C und 60°C und höchst vorzugsweise zwischen 50°C und 55°C hat.
  6. Die Tür oder das Fenster gemäß Anspruch 1, wobei es sich beim dem Schaumstoff um einen offenporigen Schaumstoff handelt.
  7. Die Tür oder das Fenster gemäß Anspruch 6, wobei der Zellendurchmesser in einem Bereich von 100 µm bis 800 µm oder kleiner liegt.
  8. Die Tür oder das Fenster gemäß Anspruch 1, wobei es sich beim dem Schaumstoff um einen wasserabweisenden Schaumstoff handelt.
  9. Die Tür oder das Fenster gemäß Anspruch 1, wobei der Polymerschaumstoff einen Dichtebereich zwischen 20 kg/m3 und 800 kg/m3, vorzugsweise zwischen 25 kg/m3 und 200 kg/m3 in expandiertem Zustand aufweist.
  10. Ein Bauteilsatz bestehend aus einem Fenster- oder Türrahmenprofil mit einer inneren Kammer (7, 8) und einem Streifen auf Formgedächtnispolymerschaum (10), wobei der Schaumstoff davon eine Tg über 20°C hat.
  11. Ein Bauteilsatz gemäß Anspruch 10, wobei der Schaumstoffstreifen (10) auf ein Querschnittmaß (Höhe oder Breite oder beides) zusammengepresst wird, das kleiner als die Querschnittmaße (Höhe oder Breite oder beides) der inneren Kammer (7, 8) des Profils (1) ist.
  12. Methode für die Herstellung eines Tür- oder Fensterprofils mit einem Formgedächtnispolymerschaum bestehend aus den folgenden Schritten:
    (a) Zusammenpressen des Schaumstoffs (9) auf ein Querschnittmaß (Höhe oder Breite oder beides), das kleiner als die Querschnittmaße (Höhe oder Breite oder beides) der inneren Kammer (7, 8) des Profils (1) ist;
    (b) Übertragung des im Schritt (a) erhaltenen zusammengepressten Schaumstoffs in die Kammer (7, 8) des Profils;
    (c) Ausdehnung des Schaumstoffs (9) in der Kammer (7, 8) des Profils.
  13. Die Methode gemäß Anspruch 12, wobei die Übertragung des zusammengepressten Schaumstoffs (10) das Einführen und/oder Einsetzen des zusammengepressten Schaumstoffs in das Profil (1) umfasst.
  14. Die Methode gemäß Anspruch 13, wobei das Einführen und Einsetzen des zusammengepressten Schaumstoffs in das Profil direkt beim Zusammenpressen erfolgt.
EP11729423.1A 2010-07-05 2011-07-05 Tür oder Fenster mit geschäumtem Einsatz, Herstellungsverfahren eines Tür- oder Fensterprofils mit solchem Schaum, und Teilesatz mit Tür- oder Fensterrahmenprofil und geschäumten Einsatz. Not-in-force EP2591196B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11729423.1A EP2591196B1 (de) 2010-07-05 2011-07-05 Tür oder Fenster mit geschäumtem Einsatz, Herstellungsverfahren eines Tür- oder Fensterprofils mit solchem Schaum, und Teilesatz mit Tür- oder Fensterrahmenprofil und geschäumten Einsatz.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP10168485A EP2405092A1 (de) 2010-07-05 2010-07-05 Rahmenprofil mit Schaumeinsatz, Verwendung eines solchen Rahmenprofils, Satz aus Teilen eines Rahmenprofils und einem Schaumeinsatz sowie Fenster oder Tür mit einem solchen Rahmenprofil
EP10173997 2010-08-25
EP11729423.1A EP2591196B1 (de) 2010-07-05 2011-07-05 Tür oder Fenster mit geschäumtem Einsatz, Herstellungsverfahren eines Tür- oder Fensterprofils mit solchem Schaum, und Teilesatz mit Tür- oder Fensterrahmenprofil und geschäumten Einsatz.
PCT/EP2011/061347 WO2012004277A1 (en) 2010-07-05 2011-07-05 Frame profile comprising foamed insert, use of such frame profile, kit of parts of a frame profile and a foam insert and window or door comprising such frame profile

Publications (2)

Publication Number Publication Date
EP2591196A1 EP2591196A1 (de) 2013-05-15
EP2591196B1 true EP2591196B1 (de) 2015-01-14

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP11728904.1A Withdrawn EP2591197A1 (de) 2010-07-05 2011-07-05 Rahmenprofil mit geschäumtem einsatz, verwendung eines derartigen rahmenprofils, teilesatz eines rahmenprofils und schaumeinsatz sowie fenster oder tür mit einem derartigen rahmenprofil
EP11729423.1A Not-in-force EP2591196B1 (de) 2010-07-05 2011-07-05 Tür oder Fenster mit geschäumtem Einsatz, Herstellungsverfahren eines Tür- oder Fensterprofils mit solchem Schaum, und Teilesatz mit Tür- oder Fensterrahmenprofil und geschäumten Einsatz.

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP11728904.1A Withdrawn EP2591197A1 (de) 2010-07-05 2011-07-05 Rahmenprofil mit geschäumtem einsatz, verwendung eines derartigen rahmenprofils, teilesatz eines rahmenprofils und schaumeinsatz sowie fenster oder tür mit einem derartigen rahmenprofil

Country Status (2)

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EP (2) EP2591197A1 (de)
WO (2) WO2012004278A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1020765A4 (nl) * 2012-06-25 2014-04-01 Recticel Nv Plaasterverband en/of orthese.
CN112627681B (zh) * 2020-12-17 2021-12-14 南通海鹰门窗安装工程有限公司 一种高保温防风型断桥铝合金门窗

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3440710A1 (de) * 1984-11-07 1986-05-07 Theodor 8857 Gottmannshofen Straub Verfahren zur herstellung von isolierprofilen aus aluminium
DE9320588U1 (de) * 1993-12-16 1994-10-06 Hueck Eduard Gmbh Co Kg Wärmegedämmtes Verbundprofil für Fenster, Türen, Fassaden o.dgl.
DE19504601C2 (de) * 1995-01-11 1998-04-09 Wicona Bausysteme Gmbh Wärmegedämmtes Verbundprofil
DE102007061883A1 (de) 2007-12-20 2009-06-25 Bayer Materialscience Ag Viskoelastischer Polyurethanschaumstoff
DE502008000451D1 (de) 2008-01-16 2010-04-29 Alcoa Aluminium Deutschland In Wärmegedämmtes Verbundprofil mit Isolierkern sowie Verfahren zur Herstellung eines solchen Verbundprofils
EP2107176B1 (de) * 2008-03-31 2015-09-30 ISO-Chemie GmbH Herstellung eines Dichtbandes aus weichem Schaumstoff
US7926565B2 (en) * 2008-10-13 2011-04-19 Baker Hughes Incorporated Shape memory polyurethane foam for downhole sand control filtration devices
DE102008063371A1 (de) * 2008-12-30 2009-12-31 Henkel Ag & Co. Kgaa Vorkomprimiertes verzögert zurückstellendes Schaumstoffdichtband zur Abdichtung von Fugen zwischen Fensterrahmen und Baukörper

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Publication number Publication date
WO2012004278A1 (en) 2012-01-12
EP2591197A1 (de) 2013-05-15
EP2591196A1 (de) 2013-05-15
WO2012004277A1 (en) 2012-01-12

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