EP1092064A1 - Method for making paper and cardboard and retention and dewatering agents - Google Patents
Method for making paper and cardboard and retention and dewatering agentsInfo
- Publication number
- EP1092064A1 EP1092064A1 EP99923647A EP99923647A EP1092064A1 EP 1092064 A1 EP1092064 A1 EP 1092064A1 EP 99923647 A EP99923647 A EP 99923647A EP 99923647 A EP99923647 A EP 99923647A EP 1092064 A1 EP1092064 A1 EP 1092064A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- emulsion
- branched
- polymer
- paper
- cardboard
- 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.)
- Granted
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
- 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
- D21H23/06—Controlling the addition
- D21H23/14—Controlling the addition by selecting point of addition or time of contact between components
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- 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
- D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
- D21H23/765—Addition of all compounds to the pulp
-
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- 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
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
Definitions
- the present invention relates to the technical sector of manufacturing paper and polymers used in this context.
- the invention relates to a process for the production of retention paper or board, and other improved properties.
- EP 0 574 335 has made an important improvement by proposing the use of polymers (in particular polyacrylamides) branched in the form of a powder.
- the invention overcomes the drawbacks mentioned above.
- the branched polyacrylamide (or more generally the branched (co) polymer) is introduced into the suspension, very preferably, in the form of a water-in-oil reverse emulsion, at a rate of 0.03 to one per thousand (0.03 to 1% o, or 30 to 1000 g / t) by weight of active material (polymer) relative to the dry weight of the fibrous suspension, preferably 0.15 to 0.5 per thousand, or 150 at 500 g / t.
- the reverse polymer emulsion is diluted with water and inverted (dissolved) by this dilution before its introduction, as described above.
- the polymer is prepared by a reverse water-in-oil emulsion polymerization.
- this polymer can then be used (ie injected or introduced into the mass or paste to be flocculated) either in the form - preferably - of this reverse emulsion after its dissolution in water, or in the form of a powder obtained by drying (in particular by spray drying or “spray drying”) of the reverse emulsion of the polymerization, then redissolution of this powder in water, for example at a concentration of the order of 5 g of active polymer / liter, the solution thus obtained is then injected into the paste at substantially the same dosages of polymer.
- the branched (co) polyacrylamide is a cationic copolymer of acrylamide and of an unsaturated cationic ethylenic monomer, chosen from the group comprising dimethylaminoethyl acrylate
- ADAME dimethylaminoethyl methacrylate
- MADAME dimethylaminoethyl methacrylate
- benzyl chloride methyl chloride, alkyl- or aryl chlorides, dimethylsulfate, dimethyldiallylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC), and methacrylamidopropyltrimethylammonium chloride (MAPTAC)
- this copolymer is branched by a branching agent consisting of a compound having at least two reactive groups chosen from the group comprising double bonds, aldehyde bonds or epoxy bonds.
- branching agent consisting of a compound having at least two reactive groups chosen from the group comprising double bonds, aldehyde bonds or epoxy bonds.
- branched polymer is a polymer which has on the chain branches, groups or branches arranged globally in a plane and not in the three directions, unlike a crosslinked polymer ( "Cross-linked”); such branched, high molecular weight polymers are well known as flocculating agents.
- Crosslinked polymer “Cross-linked”
- These branched polyacrylamides are distinguished from crosslinked polyacrylamides by the fact that in the latter, the groups are arranged three-dimensionally to lead to products which are practically insoluble and of infinite molecular weight.
- the branching may preferably be carried out during (or optionally after) the polymerization, for example by reaction of two soluble polymers having counterions, or by reaction on formaldehyde or a polyvalent metal compound. Often, the branching takes place during the polymerization by addition of a branching agent, and this solution will be clearly preferred according to the invention. These branched polymerization methods are well known.
- the branching agents which can be incorporated include ionic branching agents such as polyvalent metal salts, formaldehyde, glyoxal, or alternatively, and preferably, covalent crosslinking agents which will copolymerize with the monomers, preferably diethylenically unsaturated monomers (such as the family of diacrylate esters such as polyethylene diacrylates glycols PEG) or polyethylene, of the type conventionally used for the crosslinking of water-soluble polymers, and in particular methylenebisacrylamide (MBA) or any of the other known acrylic branching agents.
- ionic branching agents such as polyvalent metal salts, formaldehyde, glyoxal, or alternatively, and preferably, covalent crosslinking agents which will copolymerize with the monomers, preferably diethylenically unsaturated monomers (such as the family of diacrylate esters such as polyethylene diacrylates glycols PEG) or polyethylene, of the type conventionally used for the crosslinking of
- crosslinking agents are often identical to the crosslinking agents, but crosslinking can be avoided, when it is desired to obtain a branched polymer and not crosslinked, by optimizing the polymerization conditions such as concentration of polymerization, type and quantity of transfer agent, temperature, type and amount of initiators, and the like.
- the branching agent is methylene bis acrylamide (MBA), introduced at a rate of five to two hundred (5 to 200) moles per million moles of monomers, preferably 5 to 50.
- MBA methylene bis acrylamide
- the amount of branched polyacrylamide introduced into the suspension to be flocculated is between thirty and a thousand grams of active polymer / tonne of dry paste (30 and 1000 g / l), or between 0.03 per thousand and one per thousand, of preferably 150 to 500 g / l; it has been observed that if the quantity is less than 0.03% o (0.03 per thousand), no significant retention is obtained; similarly, if this quantity exceeds 1% o (1 per thousand), no proportional improvement is observed; however, unlike linear cationic polyacrylamides, as described in documents EP-A-0 017 353 and EP 0 235 893 referred to in the preamble, there is no reverse effect of dispersion by recirculation in the closed circuits of the excess polymer not retained on the sheet.
- the amount of branched polyacrylamide introduced is between 0.15 and 0.5 per thousand (0.15 and 0.5% o) of the amount of dry pulp, ie between 150 g / t and
- the branched polymer be prepared in the form of a reverse emulsion (water-in-oil) to carry out the improvement of the invention.
- emulsions and their preparation process are well known to those skilled in the art.
- the invention was all the more difficult to achieve since it is important to remain in the field of branched polymers and not to pass into the field of crosslinked polymers.
- the border between the two zones is very easily crossed, in a way that is irreversible.
- the branching zone is very narrow, we measure the difficulty of developing the invention, and it is the merit of the Applicant to have attacked the use of this technology in the field of the manufacture of paper, which poses special problems and has very strict quality requirements.
- the branched powdered polymers of the abovementioned EP 0 574 335 had already brought significant progress with regard to the properties and the process of papermaking. The improvement was around 20 to 40% depending on the properties.
- a “moderately branched” polymer will be used in a preferred, but not limiting manner, for example at 10 ppm of branching agent relative to the active material.
- the polymer may be used either in the form of its reverse synthetic emulsion, dissolved or “inverted” in water, or in the form of the solution in water of the powder obtained by drying of said synthetic emulsion, in particular by spray drying. Spray drying is a process also known to those skilled in the art. Reference will be made to the tests below to verify that the results are comparable.
- Bentonite also known as "swecting smectic clay", from the montmorillonite family, is well known and does not need to be described here in detail; these compounds, formed of microcrystallites, have sites on the surface with a high cation exchange capacity capable of retaining water (see for example document US-A-4 305 781, which corresponds to document EP-A-0 017 353 , mentioned above, and patent FR-A-2,283,102).
- a semi-sodium bentonite is used, which is introduced just upstream from the headbox, at a rate of 0.1 to 0.5 percent (0.1 to 0.5%) (0.1 0.5 percent) of the dry weight of the fibrous suspension.
- kaolins As filler, kaolins, "G CC” or ground CaC03, precipitated CaC03 or “PCC”, and the like may be used.
- the injection or introduction of the branched polymer in reverse emulsion according to the invention is carried out before a shearing step in the paper pulp (or fibrous mass to be flocculated) more or less diluted according to the practice of a person skilled in the art, and generally in diluted pulp or "thin stock", ie a pulp diluted to about 0.7 - 1.5% of solid materials such as cellulose fibers, any fillers, and the various usual additives in papermaking.
- part of the branched emulsion polymer, according to the invention will be introduced at the stage of preparation of the thick stock or “thick stock” at approx. 5% or more solids, or even in the preparation of the thick dough before a shearing step.
- the following examples illustrate the invention without, however, limiting its scope.
- the constituents of the organic phase of the emulsion to be synthesized are mixed at room temperature.
- aqueous phase of the emulsion to be prepared is prepared by mixing:
- the contents of B are mixed in A without stirring.
- the emulsion is sheared in the mixer (mixer) for 1 minute in order to create the reverse emulsion.
- the emulsion is then degassed by bubbling nitrogen then after 20 minutes, the gradual addition of metabisulfite leads to initiation and then polymerization.
- a “bum out” is carried out (metabisulfite treatment) in order to reduce the content of free monomer.
- the emulsion is then incorporated with its reverse surfactant in order to subsequently release the polymer in the aqueous phase. It will be necessary introduce 2 to 2.4% ethoxylated alcohol.
- the standard Brookfield viscosity of the said polymer will be 4.36 cps (viscosity taken at 0.1% in a 1 M NaCl solution at 25 ° C at sixty revolutions per minute)
- FO 4198 branched powder containing 20 ppm of transfer agent and 5 ppm of branching agent.
- EM140CT standard emulsion of very high molecular weight containing no branching agent.
- EM140L standard high molecular weight emulsion containing no branching agents.
- EM140LH medium molecular weight emulsion containing no branching agents.
- EM140BD crosslinked emulsion containing no transfer agent and
- SD 102 R 102 emulsion spray-dried, and powder obtained dissolved in water to 5 g of active polymer / liter.
- Ionic regain RI (X-Y) / Y x 100 with X: ionicity after shear in meq / g.
- V1 intrinsic viscosity after shearing in dl / g
- V2 intrinsic viscosity before shearing in dl / g
- Pulp used mixture of 70% KF bleached hardwood kraft
- the volume of 560 ml is introduced into the plexiglass cylinder of the automated form and the sequence is started.
- - 1 0 s, stirring start at 1500 rpm.
- - 1 10 s, addition of the polymer.
- R1 so-called second pass measurement (1st recycling)
- R2 so-called third pass measurement (2nd recycling)
- Crosslinked polymers are of no interest in the flocculation and retention of fines and fillers despite the high shear rate applied during the process to the fibrous mass (and not applied to the polymer itself), here 1500 rpm, which is characteristic of this type of microparticulate retention system. They show a low capture of colloidal charges and materials because no reduction in turbidity is observed.
- the combination with bentonite does not significantly improve the retention efficiency and only slightly improves the drainage efficiency.
- the combination according to the invention of a branched polymer in reverse emulsion and of bentonite provides a net gain in charge retention and in total retention, and appears to be superior to the known linear polymer / bentonite system.
- the coagulation power is higher for a branched emulsion polymer, which results in an excellent reduction in turbidity to 30 '(30 min.).
- Test R 52 and test R 102 show that the invention makes it possible to obtain branched products having higher UL viscosities than those accessible by gel polymerization as described in patent EP 0 574 335. Any attempt to reach such very advantageous UL viscosity values by a gel polymerization route with powder drying would lead to a product that is completely insoluble and therefore totally unusable in industry.
- the SD 102 test shows that the polymer used in the form of a solution in water of the powder obtained by drying the inverse emulsion of the synthesis of the polymer behaves like the polymer used in the form of the solution in the water of said reverse synthetic emulsion. In particular, no degradation of the polymer is observed during the spray drying step.
- the R 52 test can be usefully compared to the FO 4198 test
- the invention therefore also relates to a new retention agent for the manufacture of a sheet of paper, cardboard or the like, which consists of an acrylic (co) polymer as described above, branched, in reverse emulsion, and which is characterized in that its UL viscosity is> 3, or> 3.5 or> 4.
- Said agent can be used either as an inverted emulsion with water, or in solution of the powder obtained by drying the emulsion, as described above.
- the constituents of the organic phase of the emulsion to be synthesized are mixed at room temperature.
- phase of the emulsion to be prepared is prepared by mixing
- the contents of B are mixed in A with stirring. After mixing the phases, the emulsion is sheared in the mixer for 1 minute to create the reverse emulsion. The emulsion is then degassed by bubbling nitrogen then after 20 minutes, the gradual addition of metabisulfite leads to initiation and then polymerization.
- EK 190 standard emulsion of acrylamide co-polymer and acrylamide-propyl trimethyl ammonium chloride, linear.
- the invention also relates to the new retention agents described above, characterized in that they consist of, or comprise, at least one (co) polymer of the type described, branched, prepared in reverse emulsion, intended to cooperate with a secondary retention agent after an intermediate step of shearing of the paper pulp, as well as the processes for manufacturing sheets of paper, cardboard or the like, using the agents according to the invention or the method according to the invention, and the sheets of paper, cardboard and the like thus obtained.
- Said agent can be used either as an inverted emulsion with water, or in solution of the powder obtained by drying the emulsion, as described above.
- FO 4198 is also a powder, obtained by gel polymerization
- FO 4198 is also a powder, obtained by gel polymerization
Landscapes
- Paper (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9807144A FR2779452B1 (en) | 1998-06-04 | 1998-06-04 | PROCESS FOR PRODUCING PAPER AND CARDBOARD AND NOVEL RETENTION AND DRIPPING AGENTS THEREOF, AND PAPER AND CARDBOARD THUS OBTAINED |
FR9807144 | 1998-06-04 | ||
PCT/FR1999/001278 WO1999063159A1 (en) | 1998-06-04 | 1999-06-01 | Method for making paper and cardboard and retention and dewatering agents |
Publications (4)
Publication Number | Publication Date |
---|---|
EP1092064A1 true EP1092064A1 (en) | 2001-04-18 |
EP1092064B1 EP1092064B1 (en) | 2003-11-19 |
EP1092064B2 EP1092064B2 (en) | 2009-04-22 |
EP1092064B9 EP1092064B9 (en) | 2009-10-21 |
Family
ID=9527102
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99923647A Expired - Lifetime EP1092064B9 (en) | 1998-06-04 | 1999-06-01 | Method for making paper and cardboard |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1092064B9 (en) |
JP (1) | JP4699608B2 (en) |
KR (1) | KR100685533B1 (en) |
AT (1) | ATE254693T1 (en) |
AU (1) | AU4043999A (en) |
CA (1) | CA2334196C (en) |
DE (1) | DE69912954T3 (en) |
FR (1) | FR2779452B1 (en) |
WO (1) | WO1999063159A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2779752B1 (en) * | 1998-06-12 | 2000-08-11 | Snf Sa | PROCESS FOR PRODUCING PAPER AND CARDBOARD AND NOVEL RETENTION AGENTS THEREOF, AND PAPER AND CARDBOARD THUS OBTAINED |
DE20220979U1 (en) | 2002-08-07 | 2004-10-14 | Basf Ag | Preparation of paper, pasteboard, or cardboard involving cutting of the paper pulp, addition of microparticles of cationic polymer, e.g. cationic polyamide, and a finely divided inorganic component after the last cutting step |
MXPA04003942A (en) * | 2003-05-05 | 2007-06-29 | German Vergara Lopez | Retention and drainage system for the manufacturing of paper, paperboard and similar cellulosic products. |
FR2869626A3 (en) * | 2004-04-29 | 2005-11-04 | Snf Sas Soc Par Actions Simpli | METHOD FOR MANUFACTURING PAPER AND CARDBOARD, NEW CORRESPONDING RETENTION AND DRAINING AGENTS, AND PAPERS AND CARTONS THUS OBTAINED |
DE102004044379B4 (en) | 2004-09-10 | 2008-01-10 | Basf Ag | Process for the production of paper, paperboard and cardboard and use of a retention agent combination |
DE102004063005A1 (en) | 2004-12-22 | 2006-07-13 | Basf Ag | Process for the production of paper, cardboard and cardboard |
DE102008000811A1 (en) | 2007-03-29 | 2008-10-09 | Basf Se | Preparing paper, paperboard and cardboard, comprises shearing the paper material, adding ultrasound treated microparticle system and fine-particle inorganic component to the paper material and dewatering the paper material to form sheets |
BRPI0917678B1 (en) | 2008-09-02 | 2019-09-10 | Basf Se | process for the production of paper, cardboard and cardboard |
US9909070B2 (en) | 2009-09-15 | 2018-03-06 | Suncor Energy Inc. | Process for flocculating and dewatering oil sand mature fine tailings |
PL3199218T3 (en) | 2009-09-15 | 2020-04-30 | Suncor Energy Inc. | Process for drying oil sand mature fine tailings |
US9068776B2 (en) | 2009-10-30 | 2015-06-30 | Suncor Energy Inc. | Depositing and farming methods for drying oil sand mature fine tailings |
ES2720487T3 (en) * | 2012-02-01 | 2019-07-22 | Basf Se | Paper and cardboard manufacturing process |
GB2567456B (en) | 2017-10-12 | 2021-08-11 | Si Group Switzerland Chaa Gmbh | Antidegradant blend |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4617362A (en) * | 1984-12-31 | 1986-10-14 | Allied Corporation | Inverse emulsion polymers with improved incorporation of diallyldimethylammonium chloride |
DE3666690D1 (en) † | 1985-04-25 | 1989-12-07 | Allied Colloids Ltd | Flocculation processes |
FR2589145A1 (en) * | 1985-10-25 | 1987-04-30 | Snf Sa | Flocculating agent for the treatment of sludges based on branched water-soluble addition polymers |
GB8602121D0 (en) † | 1986-01-29 | 1986-03-05 | Allied Colloids Ltd | Paper & paper board |
US5354481A (en) † | 1988-12-19 | 1994-10-11 | Cytec Technology Corp. | Water-soluble highly branched polymeric microparticles |
ATE118224T1 (en) * | 1988-12-19 | 1995-02-15 | Cytec Tech Corp | HIGH PERFORMANCE POLYMER FLOCCULATING AGENT. |
US5405554A (en) † | 1990-02-08 | 1995-04-11 | Cytec Technology Corp. | High performance dewatering aids |
US5234548A (en) * | 1992-01-02 | 1993-08-10 | Vinings Industries Inc. | Production of paper and paperboard |
FR2692292B1 (en) * | 1992-06-11 | 1994-12-02 | Snf Sa | Method for manufacturing paper or cardboard with improved retention. |
GB9313956D0 (en) * | 1993-07-06 | 1993-08-18 | Allied Colloids Ltd | Production of paper |
GB9410920D0 (en) † | 1994-06-01 | 1994-07-20 | Allied Colloids Ltd | Manufacture of paper |
FR2740482B1 (en) * | 1995-10-30 | 1997-11-21 | Snf Sa | PROCESS FOR IMPROVING RETENTION IN A PAPER, CARDBOARD AND THE LIKE PROCESS |
SE9504081D0 (en) * | 1995-11-15 | 1995-11-15 | Eka Nobel Ab | A process for the production of paper |
JP3614609B2 (en) * | 1996-09-10 | 2005-01-26 | ハイモ株式会社 | Papermaking chemicals, papermaking methods and methods for producing papermaking chemicals |
-
1998
- 1998-06-04 FR FR9807144A patent/FR2779452B1/en not_active Expired - Lifetime
-
1999
- 1999-06-01 AT AT99923647T patent/ATE254693T1/en active
- 1999-06-01 WO PCT/FR1999/001278 patent/WO1999063159A1/en active IP Right Grant
- 1999-06-01 EP EP99923647A patent/EP1092064B9/en not_active Expired - Lifetime
- 1999-06-01 KR KR1020007013706A patent/KR100685533B1/en not_active IP Right Cessation
- 1999-06-01 DE DE69912954T patent/DE69912954T3/en not_active Expired - Lifetime
- 1999-06-01 CA CA002334196A patent/CA2334196C/en not_active Expired - Lifetime
- 1999-06-01 AU AU40439/99A patent/AU4043999A/en not_active Abandoned
- 1999-06-01 JP JP2000552347A patent/JP4699608B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9963159A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP1092064B1 (en) | 2003-11-19 |
AU4043999A (en) | 1999-12-20 |
CA2334196A1 (en) | 1999-12-09 |
DE69912954T3 (en) | 2010-01-28 |
FR2779452A1 (en) | 1999-12-10 |
FR2779452B1 (en) | 2000-08-11 |
KR20010052553A (en) | 2001-06-25 |
KR100685533B1 (en) | 2007-02-22 |
DE69912954T2 (en) | 2004-11-11 |
ATE254693T1 (en) | 2003-12-15 |
DE69912954D1 (en) | 2003-12-24 |
CA2334196C (en) | 2008-07-15 |
JP2002517626A (en) | 2002-06-18 |
JP4699608B2 (en) | 2011-06-15 |
EP1092064B2 (en) | 2009-04-22 |
EP1092064B9 (en) | 2009-10-21 |
WO1999063159A1 (en) | 1999-12-09 |
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