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EP2616578B1 - Procédé pour renforcer un non-tissé - Google Patents

Procédé pour renforcer un non-tissé Download PDF

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Publication number
EP2616578B1
EP2616578B1 EP11752567.5A EP11752567A EP2616578B1 EP 2616578 B1 EP2616578 B1 EP 2616578B1 EP 11752567 A EP11752567 A EP 11752567A EP 2616578 B1 EP2616578 B1 EP 2616578B1
Authority
EP
European Patent Office
Prior art keywords
fibers
nonwoven fabric
flat
fiber
viscose
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
EP11752567.5A
Other languages
German (de)
English (en)
Other versions
EP2616578A1 (fr
Inventor
Ingo Bernt
Walter Roggenstein
Anemone TAUTENHAHN
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.)
Kelheim Fibres GmbH
Original Assignee
Kelheim Fibres GmbH
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 Kelheim Fibres GmbH filed Critical Kelheim Fibres GmbH
Priority to EP11752567.5A priority Critical patent/EP2616578B1/fr
Publication of EP2616578A1 publication Critical patent/EP2616578A1/fr
Application granted granted Critical
Publication of EP2616578B1 publication Critical patent/EP2616578B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/44Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
    • D04H1/46Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
    • D04H1/492Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres by fluid jet
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425Cellulose series
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425Cellulose series
    • D04H1/4258Regenerated cellulose series
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4391Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
    • D04H1/43912Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres fibres with noncircular cross-sections
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4391Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
    • D04H1/43914Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres hollow fibres
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/44Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
    • D04H1/46Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06CFINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C29/00Finishing or dressing, of textile fabrics, not provided for in the preceding groups
    • D06C29/005Finishing or dressing, of textile fabrics, not provided for in the preceding groups hydroentangling

Definitions

  • the present invention relates to a method for solidifying a nonwoven fabric by means of water jet treatment.
  • the solidification of the carded fabric presented is achieved by an interweaving and turbulence of the fibers.
  • the submitted fibers are detected by the water jets, set in motion and three-dimensional entwined by a swirling movement.
  • cotton is generally considered, see e.g. the article "Aquajet spunlace process - technology for cotton fibers” by Alfred Watzl, Fa. Fleissner.
  • Aquajet spunlace process - technology for cotton fibers by Alfred Watzl, Fa. Fleissner.
  • the low wet modulus of the cotton fibers and the fact that the fiber does not have a round, smooth fiber cross section.
  • modulus of elasticity fibers with a high modulus of elasticity (hereinafter referred to as "modulus of elasticity") are suitable. These are essentially non-cellulosic fibers.
  • the present invention has as its object to provide a method for hydroentanglement of fiber webs, which is feasible with a lower energy consumption.
  • This object is achieved by a method for solidifying a nonwoven fabric by means of water jet treatment, which is characterized in that the nonwoven fabric contains flat fibers in the form of collapsed viscose hollow fibers with a ratio of width B to thickness D of B: D ⁇ 10: 1.
  • the present invention relates to a hydroentangled nonwoven fabric containing flat fibers in the form of collapsed viscose hollow fibers with a ratio of width B to thickness D of B: D ⁇ 10: 1.
  • the flat fibers contained in the nonwoven fabric preferably have a ratio B: D of 10: 1 to 30: 1, particularly preferably of 20: 1.
  • the flat fibers may preferably have a titer of 0.9 to 5 dtex, particularly preferably 1.3 to 1.9 dtex.
  • Flat fibers and their production are known.
  • Flat fibers have a substantially flat or elongated cross-section, in contrast to the usually substantially circular cross-section of fibers.
  • cellulosic flat fibers can be produced by spinning a cellulose or a cellulose derivative containing dope through slit-shaped spinnerets.
  • flat fibers may alternatively be in the form of collapsed Hollow fibers are produced.
  • a gas for example nitrogen, or a blowing agent, for example sodium carbonate, is mixed into the spinning viscose.
  • cellulosic flat fibers are for example from the GB 945,306A , of the US 3,156,605 A , of the US 3,318,990 , of the GB 1,063,217 A known.
  • Such fibers have been proposed, in part for use in papermaking, as described in part in the documents just mentioned.
  • the WO 2006/134132 describes the use of Viskoseflachmaschinen in a fiber composite with the purpose to improve the solubility of the fiber composite in water.
  • the flat fibers used have according to WO 2006/134132 preferably a krenellATORATOR (crenellated) surface, so are produced in contrast to collapsed hollow fibers by means of spinning through a slot nozzle.
  • the ribbed surface of such flat fibers reduces fiber-fiber adhesion and thus strength.
  • the achievable thickness in conventional flat fibers is limited by the nozzle geometry. When spinning with nozzles with an opening of 25 ⁇ m height results in general, a fiber thickness of about 4-6 ⁇ m. In order to consistently produce a fiber thickness of about 2-3 ⁇ m as with collapsed hollow fibers, a nozzle orifice of about 12.5 ⁇ m in height would be necessary, which is not economically viable in either nozzle making or viscose fiber production by conventional techniques.
  • the viscose flat fibers used according to the invention are collapsed hollow fibers which, as mentioned above, can be produced by introducing gas or a blowing agent (in particular sodium carbonate) into the spinning viscose.
  • the fiber can be completely collapsed or still slightly open.
  • the water retention capacity of the fiber should preferably be 200% or less (measured according to DIN 53814).
  • the fiber cross section of the fibers should be predominantly flat and preferably not branched.
  • the proportion of the flat fibers in the nonwoven fabric is preferably 5% to 100%, in particular 20% or more, particularly preferably 50% or more.
  • the nonwoven fabric can thus consist entirely of the flat fibers or else contain a mixture of the flat fibers with other fibers.
  • Suitable mixing partners are all cellulosic and non-cellulosic fiber materials which are suitable for hydroentanglement. It is clear to those skilled in the art that the effect of the present invention (i.e., increasing the strength of the web or saving energy) is the more pronounced the higher the content of the flat fibers in the web is.
  • the invention also relates to a hydroentangled nonwoven fabric comprising flat fibers in the form of collapsed viscose hollow fibers with a ratio of width B to thickness D of B: D ⁇ 10: 1.
  • a hydroentangled nonwoven fabric comprising flat fibers in the form of collapsed viscose hollow fibers with a ratio of width B to thickness D of B: D ⁇ 10: 1.
  • the fibers were presented as carded web and solidified on both sides in two passages.
  • Nonwoven fabrics with two basis weights and with two solidification stages (lighter - higher solidification) were produced from each fiber.
  • Basis weights 50g / m 2 or 80g / m 2
  • Solidification stages (solidification pressure indicated in each case as the sum of all pressures of all nozzle beams in both passages) Basis weight 50g / m 2 - slight consolidation: 65 bar Basis weight 50g / m 2 - higher consolidation: 95bar Basis weight 80g / m 2 - light consolidation: 95bar Basis weight 80g / m 2 - higher consolidation: 145bar
  • the higher solidification pressure is thus about 50% above the low solidification pressure.
  • the maximum elongation at break (with the same basis weight and with the same consolidation) is significantly lower for nonwovens made from flat fibers than for nonwoven fabric made from standard viscose fibers. This is probably due to the higher proportion of fiber-fiber bonds.
  • Nonwovens with flat fibers show, at the same experimental settings, a significantly higher MD / CD ratio than nonwovens made from standard viscose fibers.
  • the MD / CD ratio increases by reorienting the fibers in the solidification process.
  • the significantly higher MD / CD ratio of the nonwovens made of flat fibers compared to the nonwoven fabrics of standard viscose fibers at the same pressures shows the significantly higher flexibility of the flat fiber, which substantially facilitates the solidification process.
  • Table 3 Nonwoven fabric made of viscose flat fiber (according to the invention) grammage solidification stage Dry Wet Maximum tensile force [N / 5cm] Maximum tensile force [N / 5cm] MD + CD MD + CD 50 g / m 2 Light 74.1 50.1 50 g / m 2 High 72.3 54.5 80 g / m 2 Light 122.9 84.7 80 g / m 2 High 119.6 82.8
  • Table 4 Nonwoven fabric made of standard viscose fiber (comparison) grammage solidification stage Dry Wet Maximum tensile force [N / 5cm] Maximum tensile force [N / 5cm] MD + CD MD + CD 50 g / m 2 Light 54.5 37.8 50 g / m 2 High 81.3 46.0 80 g / m 2 Light 62.1 27.4 80 g / m 2 High 98.8 59.8
  • the strength of a nonwoven fabric normally correlates with the basis weight for the same consolidation.
  • the nonwoven reached only about 75% of its solidification potential in this solidification stage.
  • the example of the 80 g / m 2 nonwovens clearly shows the advantages of the use according to the invention of flat fibers in water-jet solidification.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Claims (8)

  1. Procédé pour le renforcement d'un non tissé au moyen d'un traitement par jet d'eau, caractérisé en ce que le non tissé contient des fibres plates sous la forme de fibres creuses de viscose collapsées ayant un rapport entre la largeur L et l'épaisseur E de L : E ≥ 10 : 1.
  2. Procédé selon la revendication 1, caractérisé en ce que les fibres plates présentent un rapport L : E entre 10 : 1 et 30 : 1, de préférence de 20 : 1.
  3. Procédé selon les revendications 1 ou 2, caractérisé en ce que les fibres plates présentent un titre entre 0,9 et 5 dtex, de préférence entre 1,3 et 1,9 dtex.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que la proportion de fibres plates dans le non tissé est entre 5 % et 100 %, de préférence de 20 % ou plus, de manière particulièrement préférée de 50 % ou plus.
  5. Textile non tissé, renforcé par un jet d'eau, contenant des fibres plates sous la forme de fibres creuses de viscose collapsées, ayant un rapport entre la largeur L et l'épaisseur E de L : E ≥ 10 : 1.
  6. Textile non tissé selon la revendication 5, caractérisé en ce que les fibres plates présentent un rapport L : E entre 10 : 1 et 30 : 1, de préférence de 20 : 1.
  7. Textile non tissé selon les revendications 5 ou 6, caractérisé en ce que les fibres plates présentent un titre entre 0,9 et 5 dtex, de préférence entre 1,3 et 1,9 dtex.
  8. Textile non tissé selon l'une des revendications 5 à 7, caractérisé en ce que la proportion de fibres plates dans le non tissé se situe entre 5 % et 100 %, de préférence à 20 % ou plus, de manière particulièrement préférée à 50 % ou plus.
EP11752567.5A 2010-09-14 2011-09-09 Procédé pour renforcer un non-tissé Active EP2616578B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11752567.5A EP2616578B1 (fr) 2010-09-14 2011-09-09 Procédé pour renforcer un non-tissé

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10009534A EP2428603A1 (fr) 2010-09-14 2010-09-14 Procédé pour la fixation d'une étoffe en fibres
EP11752567.5A EP2616578B1 (fr) 2010-09-14 2011-09-09 Procédé pour renforcer un non-tissé
PCT/EP2011/065621 WO2012034934A1 (fr) 2010-09-14 2011-09-09 Procédé pour renforcer un non-tissé

Publications (2)

Publication Number Publication Date
EP2616578A1 EP2616578A1 (fr) 2013-07-24
EP2616578B1 true EP2616578B1 (fr) 2014-11-12

Family

ID=43587658

Family Applications (2)

Application Number Title Priority Date Filing Date
EP10009534A Withdrawn EP2428603A1 (fr) 2010-09-14 2010-09-14 Procédé pour la fixation d'une étoffe en fibres
EP11752567.5A Active EP2616578B1 (fr) 2010-09-14 2011-09-09 Procédé pour renforcer un non-tissé

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP10009534A Withdrawn EP2428603A1 (fr) 2010-09-14 2010-09-14 Procédé pour la fixation d'une étoffe en fibres

Country Status (8)

Country Link
US (1) US20190194846A1 (fr)
EP (2) EP2428603A1 (fr)
JP (1) JP2013537263A (fr)
KR (1) KR101889112B1 (fr)
CN (1) CN103080397B (fr)
BR (1) BR112013005857B1 (fr)
IL (1) IL225101A (fr)
WO (1) WO2012034934A1 (fr)

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3173830A (en) * 1959-06-16 1965-03-16 Courtaulds Ltd Paper comprising collapsed regenerated cellulose fibers
US3156605A (en) 1960-03-25 1964-11-10 Fmc Corp Regenerated cellulose fiber
US3318990A (en) 1962-08-18 1967-05-09 Kurashiki Rayon Co Method of manufacturing flat viscose fibers
GB1063217A (en) 1962-08-25 1967-03-30 Kurashiki Rayon Kk Papers and non-woven fabrics containing mixed spun fibres
GB1064475A (en) * 1962-09-12 1967-04-05 Kurashiki Rayon Kk Paper
GB1260839A (en) * 1968-05-06 1972-01-19 Courtaulds Ltd Regenerated cellulose strips
JPS4820165B1 (fr) * 1969-10-06 1973-06-19
JPS4914423B1 (fr) * 1970-12-29 1974-04-08
JPS5013245B2 (fr) * 1972-06-10 1975-05-19
US4755421A (en) * 1987-08-07 1988-07-05 James River Corporation Of Virginia Hydroentangled disintegratable fabric
JPH0820165B2 (ja) * 1989-04-21 1996-03-04 ホシザキ電機株式会社 蓄氷式冷水供給装置
JPH08141064A (ja) * 1994-11-18 1996-06-04 Toho Rayon Co Ltd 高保水材及びその製造法
GB2309466B (en) * 1996-01-29 1999-09-08 Courtaulds Fibres A nonwoven fabric
JPH11172520A (ja) * 1997-12-08 1999-06-29 Daiwabo Rayonne Kk 中空ビスコースレーヨンの製造方法
JP4721585B2 (ja) * 2001-09-25 2011-07-13 ライオン株式会社 拭き取りシート
DE102005029597A1 (de) * 2005-06-15 2006-12-28 Kelheim Fibres Gmbh In Wasser auflösbares bzw. zersetzbares Faser- und/oder Polymermaterial
FR2899245B1 (fr) * 2006-03-28 2009-07-03 Rieter Perfojet Sa Non-tisse resistant et se delitant.
JP2008025048A (ja) * 2006-07-20 2008-02-07 Japan Vilene Co Ltd 印刷用基材

Also Published As

Publication number Publication date
KR20130139859A (ko) 2013-12-23
BR112013005857B1 (pt) 2020-07-28
EP2616578A1 (fr) 2013-07-24
EP2428603A1 (fr) 2012-03-14
WO2012034934A1 (fr) 2012-03-22
CN103080397A (zh) 2013-05-01
CN103080397B (zh) 2017-04-26
IL225101A (en) 2017-05-29
BR112013005857A2 (pt) 2016-05-17
US20190194846A1 (en) 2019-06-27
KR101889112B1 (ko) 2018-08-16
JP2013537263A (ja) 2013-09-30

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