WO2006120235A1 - Procede de fabrication d'un papier et papier fabrique selon ce procede - Google Patents

Procede de fabrication d'un papier et papier fabrique selon ce procede Download PDF

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Publication number
WO2006120235A1
WO2006120235A1 PCT/EP2006/062255 EP2006062255W WO2006120235A1 WO 2006120235 A1 WO2006120235 A1 WO 2006120235A1 EP 2006062255 W EP2006062255 W EP 2006062255W WO 2006120235 A1 WO2006120235 A1 WO 2006120235A1
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WO
WIPO (PCT)
Prior art keywords
paper
furnish
polymer
fillers
polymers
Prior art date
Application number
PCT/EP2006/062255
Other languages
English (en)
Inventor
Björn LEGNERFÄLT
Elisabeth Dolff
Jan Olausson
Original Assignee
Stora Enso Ab
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=36754154&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2006120235(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Stora Enso Ab filed Critical Stora Enso Ab
Priority to PL06755166T priority Critical patent/PL1885954T3/pl
Priority to US11/920,328 priority patent/US20090107645A1/en
Priority to BRPI0608971A priority patent/BRPI0608971B8/pt
Priority to CN2006800244851A priority patent/CN101218394B/zh
Priority to EP06755166A priority patent/EP1885954B1/fr
Priority to DK06755166.3T priority patent/DK1885954T3/da
Priority to AT06755166T priority patent/ATE497061T1/de
Priority to CA2607332A priority patent/CA2607332C/fr
Priority to DE602006019856T priority patent/DE602006019856D1/de
Publication of WO2006120235A1 publication Critical patent/WO2006120235A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D21H17/26—Ethers thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp

Definitions

  • the present invention relates to a process for the production of a paper product with high filler content wherein the furnish used is treated with polymers in steps.
  • fillers are cheaper than fibers, one way is to increase the filler content of the paper and thus be able to reduce the amount of fibers in the paper. Besides being economically beneficial, fillers also improve the opacity and printability properties of the paper. However, large amount of fillers in the paper decreases the strength of the paper. Thus, there is a balance between the possible amount of fillers added and the required strength of the paper produced.
  • Current levels of fillers in paper vary depending on paper grade, for example the filler content of newsprint may be up to about 12-14%. The maximum filler content today, considering available publication paper grades and fine paper grades, is about 35%, as it is in uncoated magazine paper.
  • One way to compensate for the decrease in strength caused when filler is added is to improve the fiber bonding properties between the fibers in the paper, thereby maintaining the strength of the paper. With increased strength of the paper it is possible to increase the filler content.
  • the predominant treatment for improving paper strength, particularly dry strength, of paper has so far been to add a strength agent, preferably cationic starch, to the pulp fiber slurry prior to the sheet forming operation.
  • a strength agent preferably cationic starch
  • cationic starch molecules tend to saturate the anionic charge on the cellulose fibers, thus setting a limit to the amount of cationic starch which can be added to the slurry. If an excess of cationic starch is added, only a portion of the starch added will be retained in the sheet, and the rest will circulate in the paper or board machine white water system.
  • a second problem is that fibers which are made cationic by excessive cationic starch addition, will not be able to adsorb other cationic additives which are commonly added to the pulp slurry, such as sizing agents and retention aids.
  • Another method to enhance the strength properties of paper is to treat the fibers with polymers in consecutive steps.
  • the international application WO 2006041401 describes such method where a part of a furnish is treated with polymers in consecutive steps, whereby a paper or board with improved strength and with reduced amount of polymers is obtained.
  • the object of the invention is to provide a process by which a paper product having a high strength can be produced at low cost.
  • the present invention concerns a process for the production of a paper product, which process comprises providing a furnish comprising fillers and fibers; subjecting the furnish to polymer treatment, in which polymers are added to the furnish in at least three steps; dewatering the furnish on a wire to form a fiber web, pressing said fiber web and drying the fiber web to form said paper product; said furnish containing fillers in such an amount that the paper product obtained by the process contains at least 15% by weight of fillers .
  • a paper product with high strength is obtained.
  • the paper product produced preferably contains 15-70% fillers by weight of the total paper weight.
  • the polymer used in each of the consecutive polymer treatment steps is preferably interacting with the polymer used in the subsequent step.
  • the polymer treatment preferably includes one step in which cationic polymer is added, and at least one step in which anionic polymer is added. By alternating cationic and anionic polymer additions it is believed that interacting polymer layers are obtained.
  • the cationic polymer is preferably cationic starch and the anionic polymer is preferably CMC.
  • the polymer treatment preferably comprises three to seven consecutive steps.
  • the invention also relates to a paper product produced according to the process of the present invention.
  • the invention relates to a process for the production of a paper product from a furnish comprising fillers and fibers, wherein the furnish is treated with polymers in at least three steps and of which said furnish contains fillers in such an amount that the paper product produced contains at least 15% by weight of fillers.
  • the invention also relates to a paper product produced according to the process of the present invention.
  • the present process for producing a paper or board product comprises, providing a furnish comprising fillers and fibers; subjecting the furnish to polymer treatment, in which polymers are added to the furnish in at least three steps; dewatering the furnish on a wire to form a fiber web; pressing said fiber web and drying the fiber web to form said paper product; said furnish containing fillers in such an amount that the paper product obtained by the process contains at least 15% by weight of fillers.
  • the filler content of the paper product is at least 15% by weight of the total paper sheet weight, preferably 15-70% and even more preferably 20-70% or 20-50% by weight, since it has been seen that the strength of the paper still is high, even if the filler content is increased, and it thus makes it possible to produce a paper product at lower cost.
  • the filler content is even more preferably between 30-50% by weight since the strength of the paper is good even at this high filler content, this can bee seen in table 1.
  • the filler content is adjusted in order to achieve the desired strength of the paper product. It is desirable to have as high filler content as possible without decreasing the strength to unacceptable levels.
  • the appropriate amount of fillers depends on the properties of the furnish and on the quality demands of the paper product.
  • the amount of fillers added to the furnish, in order to receive a paper product with a desired filler content, depends on the filler retention of the fiber web, i.e. how much of the added fillers that are retained in the resulting paper product.
  • the filler retention varies a lot and there are many factors that affect it, some examples are: the grammage of the paper, the formation unit of the paper machine, the fiber components of the furnish and the use and amount of added retention agents. Consequently, there is a wide range of what the filler retention can be, normally the filler retention is about 20-70%, i.e. 20-70% of the added fillers are retained in the paper product.
  • the polymer used in each of the consecutive polymer treatment steps is preferably interacting with the polymer used in the subsequent step, thereby enabling a larger amount of polymers to be attached to the fillers and fibers and thus result in increased strength of the final paper product.
  • the polymer treatment preferably includes one step in which anionic polymer is added, and at least one step in which cationic polymer is added. By alternating anionic and cationic polymer coatings interacting polymer layers may be obtained.
  • the anionic polymer used may be one or more chosen from the group consisting of: carboxy methyl cellulose (CMC), polyvinyl sulphate, anionic galactoglucomannan, anionic starch, polyphosphoric acid, alginate and polymethacrylic acid.
  • CMC carboxy methyl cellulose
  • the anionic polymer is preferably CMC, since it has high charge density, which reduces the amount of CMC needed in each addition, and which is therefore economically beneficial.
  • CMC also interacts very well with cationic polymers, and especially cationic starch. Thus, the use of CMC is very economically beneficial both due to its low price as well as the reduced amount needed.
  • the cationic polymer used may be one or more chosen from the group consisting of: cationic starch, polyvinyl amine, chitosan, primary and secondary amines, polyethylene imines, polyvinyl pyrrolidone and modified polyacryl amides.
  • the cationic polymer is preferably cationic starch, which is advantageous because it results in a paper having enhanced strength properties and it is economically beneficial, due to its low price and easy availability. It is preferable to use cationic starch in combination with CMC since these two polymers have been found to interact well with each other, resulting in paper with good strength at a low cost.
  • the polymer treatment preferably comprises three to seven consecutive steps. The optimal number of steps depends on what properties of the paper that are desired and on the properties of the furnish being treated. The more steps the treatment consists of, the larger amount of polymers are added and thus retained in the paper.
  • the furnish need not be washed between each polymer treatment steps. Any unabsorbed excess of polymer added in the preceding step can remain in the furnish and need not be rinsed away. Washing between the polymer treatment steps has not been shown to enhance the properties of the resulting product. It is thus advantageous to subject the furnish to each of the polymer treatment steps without any intermediate washing. Thereby, washing between the polymer treatment steps is unnecessary and may be excluded, thus a faster process is achieved which, in addition, has lower water consumption.
  • each polymer treatment step there should be sufficient time and mixing for the polymer to be absorbed to the fillers and fibers of the furnish.
  • a time period of at least 5 seconds between each polymer treatment step is suitable. The optimal time period depends on the capacity of the mixing of the equipment.
  • the polymer of each polymer treatment step can be added to the furnish in a pulp vessel, such as a pulp chest, or in-line in a furnish transport pipe, or a combination thereof.
  • the point of addition of the polymer depends on the equipment available and where it is practically possible to make the addition.
  • an in-line mixer can be used to ensure good mixing in the pipe.
  • the amount of polymer to be added varies depending of the properties of the furnish.
  • the amount of cationic starch added in each step is typically between 5-30 kg/ton and the amount of CMC added in each step is typically between 0.25-3 kg/ton.
  • the amount of polymers added to the furnish may be decided by measuring the charge of the pulp or the process water. Even if an excess amount of added polymer is not detrimental to the final result, it may be advantageous to add an amount of polymer that is close to what can be absorbed by the pulp, both for economical and environmental reasons. However, for some paper products it has been seen that an excess of polymers added to the furnish results in an improved paper product, i.e. a stronger product or a product with higher filler content with remained strength. This might be explained by that the polymers form polyelectrolyte complexes that could have favorable affects on the properties of the paper product.
  • the furnish typically contains a mixture of different kinds of pulp, for example chemical pulp (hardwood pulp, softwood pulp, sulphate pulp or sulfite pulp) or mechanical pulp (CTMP or TMP).
  • chemical pulp hardwood pulp, softwood pulp, sulphate pulp or sulfite pulp
  • CMP mechanical pulp
  • fillers used in the furnish are; kaolin, calcium carbonate, precipitated calcium carbonate, talcum, gypsum and synthetic fillers.
  • the paper product produced can be of any paper grade at any grammage, for example fine paper, magazine paper or newsprint. If necessary, additional generally known paper process steps, such as coating and calendering, can be used in order to produce the paper product according to claim 1.
  • the furnish used was a mixture of groundwood and kraft pulp in the ratio 2.5: 1.
  • Clay was used as filler and the filler content of the paper product was either 30% or 50%.
  • some samples were treated with cationic starch in one step and the other samples were treated with cationic starch and CMC in consecutive steps according to the invention.
  • the three sequential steps of the polymer treatment were: I. addition of cationic starch to the furnish sample;
  • the charge of the furnish was measured after each addition, and the amount of polymer added in each subsequent step was decided based on these measurements.
  • the polymers were added in excess as compared to the amount determined on basis of the charge measurement.
  • samples 1-6 only the fiber part was subjected to polymer treatment and thereafter fillers were added, and the fibers and fillers were mixed into a furnish. Samples 7-
  • Sheets were then prepared by dewatering the furnish, pressing and drying the fiber web and the density (ISO 5270), tensile index (ISO 5270) and z-strength (SCAN P 80) were determined for all sheets. Prior to testing the sheets were conditioned at 23°C/50% RH. The results are shown in Table 1.
  • Table 1 shows an increase in z-strength and tensile index for the resulting paper product when the entire furnish is subjected to polymer treatment, as compared to if only the fiber part of the furnish were treated. It can also be seen that treatment with polymers in consecutive steps improves both the z-strength and the tensile index.
  • the density was also measured and it can be seen that in many cases there is an increase of density as the amount of starch in the sheet increases. However, the density increase is not large enough to explain the increase of tensile index.
  • Diagram 2 and Diagram 3.
  • the abbreviation st, as can bee seen in the diagrams stands for addition of cationic starch in kg/ton.
  • the results of the z-strength measurements are shown in Diagram 1.
  • Diagram 1 shows that the z-strength of the paper sheets increases when the entire furnish is treated with polymers. The highest z-strength can be found when the furnish is treated with polymers in consecutive steps according to the invention. Surprisingly, the z-strength of the paper sheets with a filler content of 50% is very high.
  • Diagram 2 shows that the tensile index of the paper sheets increases when the entire furnish is treated with polymers. The highest value of the tensile index can be found when the furnish is treated with polymers in consecutive steps according to the invention.
  • Diagram 3 shows the tensile index compared to the amount of starch in the paper sheets.
  • Diagram 3 shows that the tensile index of the sheets is best for those sheets for which the entire furnish was treated with polymers, even if the amount of starch in the sheets is not so high.
  • the tensile index of sheets with a filler content of 50% where the entire furnish has been treated is comparable to the sheets with a filler content of 30% where only the fiber part of the furnish has been treated with polymers.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Abstract

L'invention concerne un procédé de fabrication de papier à partir d'une composition de fabrication comprenant des charges et des fibres, ladite composition de fabrication étant traitée par des polymères en au moins trois étapes, et ladite composition de fabrication contenant des charges en quantité telle que le produit papier obtenu par le procédé contienne au moins 15 % en poids de charges. L'invention concerne également un produit papier fabriqué selon le procédé de la présente invention.
PCT/EP2006/062255 2005-05-11 2006-05-11 Procede de fabrication d'un papier et papier fabrique selon ce procede WO2006120235A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
PL06755166T PL1885954T3 (pl) 2005-05-11 2006-05-11 Sposób wytwarzania papieru i papier wytworzony tym sposobem
US11/920,328 US20090107645A1 (en) 2005-05-11 2006-05-11 Process for the Production of a Paper and a Paper Produced According to the Process
BRPI0608971A BRPI0608971B8 (pt) 2005-05-11 2006-05-11 processo para a produção de um papel e um papel produzido de acordo com o processo
CN2006800244851A CN101218394B (zh) 2005-05-11 2006-05-11 纸张的生产方法以及根据该方法生产得到的纸张
EP06755166A EP1885954B1 (fr) 2005-05-11 2006-05-11 Procede de fabrication d'un papier et papier fabrique selon ce procede
DK06755166.3T DK1885954T3 (da) 2005-05-11 2006-05-11 Fremgangsmåde til fremstilling af et papir samt et papir fremstillet i henhold til fremgangsmåden
AT06755166T ATE497061T1 (de) 2005-05-11 2006-05-11 Verfahren zur herstellung eines papiers und ein danach hergestelltes papier
CA2607332A CA2607332C (fr) 2005-05-11 2006-05-11 Procede de fabrication d'un papier et papier fabrique selon ce procede
DE602006019856T DE602006019856D1 (de) 2005-05-11 2006-05-11 Verfahren zur herstellung eines papiers und ein danach hergestelltes papier

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US67973405P 2005-05-11 2005-05-11
US60/679,734 2005-05-11

Publications (1)

Publication Number Publication Date
WO2006120235A1 true WO2006120235A1 (fr) 2006-11-16

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ID=36754154

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Application Number Title Priority Date Filing Date
PCT/EP2006/062255 WO2006120235A1 (fr) 2005-05-11 2006-05-11 Procede de fabrication d'un papier et papier fabrique selon ce procede

Country Status (13)

Country Link
US (1) US20090107645A1 (fr)
EP (1) EP1885954B1 (fr)
CN (1) CN101218394B (fr)
AT (1) ATE497061T1 (fr)
BR (1) BRPI0608971B8 (fr)
CA (1) CA2607332C (fr)
DE (1) DE602006019856D1 (fr)
DK (1) DK1885954T3 (fr)
ES (1) ES2358529T3 (fr)
PL (1) PL1885954T3 (fr)
PT (1) PT1885954E (fr)
RU (1) RU2388863C2 (fr)
WO (1) WO2006120235A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102154925A (zh) * 2010-12-31 2011-08-17 陕西科技大学 一种防近视纸的生产方法
CN102639788A (zh) * 2009-12-03 2012-08-15 斯托拉恩索公司 纸或纸板产品的制造方法
US8404083B2 (en) 2008-08-18 2013-03-26 Basf Se Process for increasing the dry strength of paper, board and cardboard
WO2013132021A1 (fr) * 2012-03-09 2013-09-12 Philip Morris Products S.A. Matériau de type feuille de masse volumique réduite
WO2015036932A1 (fr) 2013-09-13 2015-03-19 Stora Enso Oyj Carton multicouche
WO2015036930A1 (fr) 2013-09-13 2015-03-19 Stora Enso Oyj Carton multicouche
US10145068B2 (en) 2014-04-29 2018-12-04 Stora Enso Oyj Process for producing at least one ply of a paper or board and a paper or board produced according to the process
US10968540B2 (en) 2015-10-08 2021-04-06 Stora Enso Oyj Process for the manufacture of a shaped body
US11365517B2 (en) 2018-03-22 2022-06-21 Kemira Oyj Method for manufacturing a multi-layered paperboard, multi-layered paperboard and composition for use in multi-layered paperboard manufacturing

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AU2008225921A1 (en) 2007-03-15 2008-09-18 Basf Se Heat-sensitive coating compositions based on resorcinyl triazine derivatives
KR20100077149A (ko) * 2007-08-22 2010-07-07 바스프 에스이 레이저-감응성 코팅 조성물
US8900414B2 (en) * 2007-11-07 2014-12-02 Datalase, Ltd. Fiber products
JP5645832B2 (ja) 2008-10-27 2014-12-24 データレース リミテッドＤａｔａｌａｓｅ Ｌｔｄ． 基材にマーキングするためのレーザー感受性水性組成物
SE1050985A1 (sv) * 2010-09-22 2012-03-23 Stora Enso Oyj En pappers eller kartongprodukt och en process förtillverkning av en pappers eller en kartongprodukt
WO2017118929A1 (fr) * 2016-01-05 2017-07-13 Stora Enso Oyj Procédé de formation d'un composite comprenant de la mfc et composite produit par le procédé
CN107620773B (zh) 2016-07-15 2021-03-19 博格华纳公司 摩擦材料
PL3516112T3 (pl) * 2016-09-26 2021-11-08 Kemira Oyj Kompozycja zwiększająca wytrzymałość na sucho, jej zastosowanie i sposób wytwarzania papieru, tektury lub tym podobnych
BE1026476B1 (nl) * 2018-07-17 2020-02-19 Anheuser Busch Inbev Sa Proces voor het produceren van papier of bordpapier, meer specifiek etiketpapier of -bordpapier dat kan worden gebruikt als verpakkingsmateriaal voor drankcontainers
DE102021005047A1 (de) 2021-10-08 2023-04-13 Factum Consult Gmbh Polyelektrolytsystem, Zusammensetzung mit einem Polyelektrolytsystem und Verfahren zur Herstellung

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US5185062A (en) * 1991-01-25 1993-02-09 Nalco Chemical Company Papermaking process with improved retention and drainage
US5736008A (en) * 1993-04-08 1998-04-07 Congoleum Corporation Fibrous-reinforced sheet
EP0790351A2 (fr) * 1996-02-14 1997-08-20 Nalco Chemical Company Procédé de fabrication de papier à l'aide d'un agent de rétention et d'égouttage multipolymère
US20020096289A1 (en) * 2000-08-07 2002-07-25 Sten Frolich Process for the production of paper
WO2006041401A1 (fr) * 2004-10-15 2006-04-20 Stora Enso Ab Procede de production de papier ou de carton et produit resultant

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8404083B2 (en) 2008-08-18 2013-03-26 Basf Se Process for increasing the dry strength of paper, board and cardboard
CN102639788A (zh) * 2009-12-03 2012-08-15 斯托拉恩索公司 纸或纸板产品的制造方法
CN102154925A (zh) * 2010-12-31 2011-08-17 陕西科技大学 一种防近视纸的生产方法
WO2013132021A1 (fr) * 2012-03-09 2013-09-12 Philip Morris Products S.A. Matériau de type feuille de masse volumique réduite
WO2015036932A1 (fr) 2013-09-13 2015-03-19 Stora Enso Oyj Carton multicouche
WO2015036930A1 (fr) 2013-09-13 2015-03-19 Stora Enso Oyj Carton multicouche
US10145068B2 (en) 2014-04-29 2018-12-04 Stora Enso Oyj Process for producing at least one ply of a paper or board and a paper or board produced according to the process
US10968540B2 (en) 2015-10-08 2021-04-06 Stora Enso Oyj Process for the manufacture of a shaped body
US11365517B2 (en) 2018-03-22 2022-06-21 Kemira Oyj Method for manufacturing a multi-layered paperboard, multi-layered paperboard and composition for use in multi-layered paperboard manufacturing

Also Published As

Publication number Publication date
EP1885954B1 (fr) 2011-01-26
BRPI0608971B8 (pt) 2017-03-21
EP1885954A1 (fr) 2008-02-13
ATE497061T1 (de) 2011-02-15
BRPI0608971A2 (pt) 2010-02-17
CN101218394B (zh) 2011-08-03
DK1885954T3 (da) 2011-03-21
PL1885954T3 (pl) 2011-07-29
BRPI0608971B1 (pt) 2016-11-01
CN101218394A (zh) 2008-07-09
DE602006019856D1 (de) 2011-03-10
PT1885954E (pt) 2011-03-17
ES2358529T3 (es) 2011-05-11
US20090107645A1 (en) 2009-04-30
RU2007145719A (ru) 2009-06-20
RU2388863C2 (ru) 2010-05-10
CA2607332C (fr) 2016-02-16
CA2607332A1 (fr) 2006-11-16

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