EP1092064B9 - Procede de fabrication de papier et carton - Google Patents

Procede de fabrication de papier et carton Download PDF

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Publication number
EP1092064B9
EP1092064B9 EP99923647A EP99923647A EP1092064B9 EP 1092064 B9 EP1092064 B9 EP 1092064B9 EP 99923647 A EP99923647 A EP 99923647A EP 99923647 A EP99923647 A EP 99923647A EP 1092064 B9 EP1092064 B9 EP 1092064B9
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EP
European Patent Office
Prior art keywords
emulsion
polymer
branched
process according
water
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.)
Expired - Lifetime
Application number
EP99923647A
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German (de)
English (en)
French (fr)
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EP1092064B1 (fr
EP1092064B2 (fr
EP1092064A1 (fr
Inventor
René Hund
Christian Snf S.A. Jehn-Rendu
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SNF SA
Original Assignee
SNF SA
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Publication date
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Application filed by SNF SA filed Critical SNF SA
Publication of EP1092064A1 publication Critical patent/EP1092064A1/fr
Publication of EP1092064B1 publication Critical patent/EP1092064B1/fr
Publication of EP1092064B2 publication Critical patent/EP1092064B2/fr
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Publication of EP1092064B9 publication Critical patent/EP1092064B9/fr
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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 papermaking.
  • the invention relates to a method for the production of paper or cardboard retention, and other properties, improved.
  • bentonite to the paste, which may optionally be added to other mineral products, such as aluminum sulphates, or even synthetic polymers, in particular polyethylene imine (see for example documents DE-A-2,262,906 and US-A-2,368,635 ).
  • EP 0 574 335 a a major improvement by proposing the use of polymers (especially polyacrylamides) branched in the form of a powder.
  • the invention overcomes the disadvantages mentioned above.
  • This method makes it possible to obtain a markedly improved retention of fines and fillers without any reverse effect.
  • An additional feature of this improvement is also improved the dewatering properties.
  • 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 inverse emulsion, at a rate of 0.03 to one per thousand. (0.03 to 1% o, ie 30 to 1000 g / t) by weight of active ingredient (polymer) relative to the dry weight of the fibrous suspension, preferably from 0.15 to 0.5 per thousand, ie 150 at 500 g / t.
  • the inverse polymer emulsion is diluted with water and inverted (solubilized) by this dilution before its introduction, as described above.
  • the polymer is prepared by water-in-oil inverse 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 inverse 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 inverse emulsion of the polymerization, and then redissolving this powder in water, for example at a concentration of the order of 5 g of active polymer / liter, the solution thus obtained being then injected into the dough at substantially the same polymer dosages.
  • the branched (co) polyacrylamide is a cationic copolymer of acrylamide and an unsaturated cationic ethylenic monomer selected from the group comprising dimethylaminoethyl acrylate (ADAME), dimethylaminoethyl methacrylate (MADAME), quaternized or salified by different quaternizing acids and agents, benzyl chloride, methyl chloride, alkyl- or aryl chlorides, dimethyl sulphate, dimethyldiallylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC), and methacrylamidopropyltrimethylammonium chloride (MAPTAC),
  • ADAME dimethylaminoethyl acrylate
  • MADAME dimethylaminoethyl methacrylate
  • benzyl chloride methyl chloride, alkyl- or aryl chlorides, dimethyl sulphate, dimethyldially
  • this copolymer is branched by a branching agent consisting of a compound having at least two reactive groups selected from the group comprising double bonds, aldehyde bonds or epoxy bonds.
  • branching agent consisting of a compound having at least two reactive groups selected from the group comprising double bonds, aldehyde bonds or epoxy bonds.
  • a branched polymer is a polymer which has branches, groups or branches on the chain which are generally arranged 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 flocculants.
  • Crosslinked polymer "Cross-linked”
  • These branched polyacrylamides are distinguished from the crosslinked polyacrylamides in that in the latter, the groups are arranged three-dimensionally to give substantially insoluble products of infinite molecular weight.
  • the branching may preferably be carried out during (or possibly after) the polymerization, for example by reaction of two soluble polymers having counterions, or by reaction with 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 branching polymerization processes are well known.
  • Branching agents which can be incorporated include ionic branching agents such as polyvalent metal salts, formaldehyde, glyoxal, or preferably covalent crosslinking agents which will copolymerize with the monomers, preferably diethylenically unsaturated monomers (such as the family of diacrylate esters such as PEG polyethylene glycol diacrylates) 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 preferably covalent crosslinking agents which will copolymerize with the monomers, preferably diethylenically unsaturated monomers (such as the family of diacrylate esters such as PEG polyethylene glycol diacrylates) or polyethylene, of the type conventionally used for the crosslinking of water-soluble polymers, and in particular methylenebis
  • crosslinking agents are often identical to the crosslinking agents, but the crosslinking can be avoided, when it is desired to obtain a branched and not crosslinked polymer, by an optimization of the polymerization conditions such as concentration during the polymerization, type and amount of polymerization. transfer agent, temperature, type and amount of initiators, and the like.
  • the branching agent is methylenebisacrylamide (MBA), introduced at a rate of five to two hundred (5 to 200) moles per million moles of monomers, preferably 5 to 50 moles.
  • MBA methylenebisacrylamide
  • the amount of branched polyacrylamide introduced into the suspension to be flocculated is between thirty and thousand grams of active polymer / tonne of dry pulp (30 and 1000 g / t), or between 0.03 per thousand and one per thousand, of preferably from 150 to 500 g / t; it has been observed that if the amount is less than 0.03% o (0.03 per thousand), no significant retention is obtained; likewise, if this quantity exceeds 1% o (1 per thousand), no proportional improvement is observed; however, unlike linear cationic polyacrylamides, as described in the 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 quantity of the dry pulp, ie between 150 g / t and 500
  • the branched polymer be prepared as an inverse emulsion (water-in-oil) to achieve the improvement of the invention.
  • emulsions and their method of preparation are well known to those skilled in the art.
  • the invention was all the more difficult to realize that it is important to remain in the field of branched polymers and not to go into the field of crosslinked polymers.
  • the border between the two zones is very easily crossed, in fact irreversibly.
  • the difficulty of developing the invention is measured, and it is the Claimant's merit that it has tackled the use of this technology in the field of manufacturing the paper, which poses particular problems and presents very stringent quality requirements.
  • the branched powdered polymers of the aforementioned EP 0 574 335 had already made significant progress with regard to the properties and the papermaking process.
  • the improvement was of the order of 20 to 40% depending on the properties.
  • a “moderately branched" polymer for example 10 ppm branching with respect to the active material, will be used in a preferred manner, but not limited to.
  • the polymer either in the form of its synthetic inverse emulsion, dissolved or "inverted” in water, or in the form of the solution in the water of the powder obtained by drying the said synthetic emulsion, in particular by spray drying.
  • Spray drying is a method also known to those skilled in the art. Refer to the tests below to verify that the results are comparable.
  • Bentonite also called “swelling smectic clay", of the montmorillonite family, is well known and there is no need to describe it here in detail; these compounds, formed of microcrystallites, have on the surface sites with a high cation exchange capacity that can retain water (see for example document US-A-4,305,781 , which corresponds to the document EP-A-0 017 353 , mentioned above, and the FR-A-2,283,102 ).
  • a semi-sodium bentonite which is introduced just upstream of the headbox, is preferably used at a rate of 0.1 to 0.5 percent (0.1 to 0.5%) of the dry weight of the fibrous suspension.
  • filler use may be kaolins, ground “GCC” or CaCO3, precipitated CaCO3 or "PCC”, and the like.
  • Injection or introduction of the branched polymer in inverse emulsion 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 the person skilled in the art, and generally in the pulp.
  • thin paper ie a pulp diluted to about 0.7 - 1.5% solids such as cellulose fibers, optional fillers, and the various conventional papermaking additives.
  • fractionally introduced will be introduced a portion of the emulsion branched polymer, according to the invention, at the stage of preparation of the thick paste or "thick stock” to approx. 5% or more solids, or even in the preparation of the thick slurry before a shear step.
  • the UL viscosity results are as follows:
  • EM140CT standard emulsion of very high molecular weight containing no branching agent.
  • EM140L standard high molecular weight emulsion containing no branching agent.
  • EM140LH Medium molecular weight emulsion containing no branching agent.
  • EM140BD crosslinked emulsion containing no transfer agent and 5 ppm crosslinking agent.
  • SD 102 spray-dried emulsion R 102, and powder obtained dissolved in water at 5 g of active polymer / liter.
  • the paste used is diluted to a consistency of 1.5%. 2.24 g of pulp are taken, ie 149 g of pulp at 150% and then diluted to 0.4% with clear water.
  • the crosslinked polymers 1, 4, 9, 12 are not of interest for the flocculation and retention of fines and fillers despite the high rate of shear applied during processing on 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 the charges and colloidal materials because no reduction of turbidity is observed.
  • the combination with bentonite does not significantly improve retention efficiency and only slightly improves drainage efficiency.
  • the combination according to the invention of a branched polymer in inverse emulsion and bentonite provides a net gain in charge retention and total retention, and is found to be superior to the known linear polymer / bentonite system.
  • the coagulation power is higher for a branched polymer in emulsion, which results in an excellent reduction of the turbidity at 30 '(30 min.).
  • the R 52 test and the R 102 test show that the invention makes it possible to obtain branched products having higher UL viscosities than those accessible by a gel polymerization as described in US Pat. EP 0 574 335 (FO 4198). Any attempt to achieve such highly advantageous UL viscosity values by a powdered gel polymerization route would result in a product that is completely insoluble and therefore totally unusable in the industry.
  • Test SD 102 shows that the polymer used in the form of a solution in the water of the powder obtained by drying the inverse emulsion of the synthesis of the polymer behaves as the polymer used in the form of the solution in the water of said synthesis inverse emulsion. In particular, there is no degradation of the polymer during the spray drying step.
  • test R 52 can be usefully compared to the test FO 4198 (powder) because the polymers have the same chemistry, therefore the same cationicity, and the same% MBA, while the R 52 used according to the invention is very higher than the powder in terms of dripping and retention (96.3 to be closer to 83.6); the NTU turbidity will also be compared after 30 minutes. , of 32 compared to 75 NTU units.
  • the invention therefore relates to a method for producing a sheet of paper or cardboard or the like, using a retention agent, which consists of an acrylic (co) polymer as described above, branched, in inverse emulsion, and which is characterized in that its UL viscosity is> 3, or> 3.5 or> 4.
  • Said agent can be used either in inverted emulsion with water, or in solution of the powder obtained by drying the emulsion, as described above.
  • the contents of B are mixed in A with stirring. After mixing the phases, the emulsion is sheared for 1 minute in order to create the inverse emulsion. The emulsion is then degassed by bubbling nitrogen and after 20 minutes, the gradual addition of metabisulfite leads to initiation and then polymerization.
  • the emulsion is then incorporated with its reversing surfactant in order subsequently to release the polymer in the aqueous phase.
  • the invention relates to a method for producing a sheet of paper or cardboard or the like employing retention agents described above, characterized in that they consist of, or comprise, at least one (co) polymer of the type described, branched, prepared in inverse emulsion, intended to cooperate with a secondary retention agent after an intermediate step of shearing the paper pulp, as well as processes for producing sheets of paper, cardboard or the like, using the agents described above in the process according to the invention, and the sheets of paper, cardboard and the like thus obtained.
  • retention agents described above consist of, or comprise, at least one (co) polymer of the type described, branched, prepared in inverse emulsion, intended to cooperate with a secondary retention agent after an intermediate step of shearing the paper pulp, as well as processes for producing sheets of paper, cardboard or the like, using the agents described above in the process according to the invention, and the sheets of paper, cardboard and the like thus obtained.
  • Said agent may be used either in inversion emulsion with water, or in solution of the powder obtained by drying the emulsion, as described above.

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  • Paper (AREA)
EP99923647A 1998-06-04 1999-06-01 Procede de fabrication de papier et carton Expired - Lifetime EP1092064B9 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9807144A FR2779452B1 (fr) 1998-06-04 1998-06-04 Procede de fabrication de papier et carton et nouveaux agents de retention et d'egouttage correspondants, et papiers et cartons ainsi obtenus
FR9807144 1998-06-04
PCT/FR1999/001278 WO1999063159A1 (fr) 1998-06-04 1999-06-01 Procede de fabrication de papier et carton et agents de retention et d'egouttage

Publications (4)

Publication Number Publication Date
EP1092064A1 EP1092064A1 (fr) 2001-04-18
EP1092064B1 EP1092064B1 (fr) 2003-11-19
EP1092064B2 EP1092064B2 (fr) 2009-04-22
EP1092064B9 true EP1092064B9 (fr) 2009-10-21

Family

ID=9527102

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99923647A Expired - Lifetime EP1092064B9 (fr) 1998-06-04 1999-06-01 Procede de fabrication de papier et carton

Country Status (9)

Country Link
EP (1) EP1092064B9 (ja)
JP (1) JP4699608B2 (ja)
KR (1) KR100685533B1 (ja)
AT (1) ATE254693T1 (ja)
AU (1) AU4043999A (ja)
CA (1) CA2334196C (ja)
DE (1) DE69912954T3 (ja)
FR (1) FR2779452B1 (ja)
WO (1) WO1999063159A1 (ja)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2779752B1 (fr) * 1998-06-12 2000-08-11 Snf Sa Procede de fabrication de papier et carton et nouveaux agents de retention correspondants, et papiers et cartons ainsi obtenus
DE20220979U1 (de) 2002-08-07 2004-10-14 Basf Ag Papierprodukt
MXPA04003942A (es) * 2003-05-05 2007-06-29 German Vergara Lopez Un sistema de retencion y drenaje recomendado para la fabricacion de papel, cartulina, carton y otros productos similares.
FR2869626A3 (fr) * 2004-04-29 2005-11-04 Snf Sas Soc Par Actions Simpli Procede de fabrication de papier et carton, nouveaux agents de retention et d'egouttage correspondants, et papiers et cartons ainsi obtenus
DE102004044379B4 (de) 2004-09-10 2008-01-10 Basf Ag Verfahren zur Herstellung von Papier, Pappe und Karton und Verwendung einer Retentionsmittelkombination
DE102004063005A1 (de) 2004-12-22 2006-07-13 Basf Ag Verfahren zur Herstellung von Papier, Pappe und Karton
DE102008000811A1 (de) 2007-03-29 2008-10-09 Basf Se Verfahren zur Herstellung von Papier
CA2735371C (en) 2008-09-02 2013-10-15 Basf Se Method for manufacturing paper, board and cardboard using endo-beta-1,4-glucanases as drainage aids
CA2701317C (en) 2009-09-15 2016-08-23 Suncor Energy Inc. Process for flocculating and dewatering oil sand mature fine tailings
EP2477707B8 (en) 2009-09-15 2017-07-26 Suncor Energy Inc. Process for drying fine tailings
AU2009354586A1 (en) 2009-10-30 2012-05-24 Suncor Energy Inc. Depositing and farming methods for drying oil sand mature fine tailings
US9404223B2 (en) * 2012-02-01 2016-08-02 Basf Se Process for the manufacture of paper and paperboard
GB2567456B (en) 2017-10-12 2021-08-11 Si Group Switzerland Chaa Gmbh Antidegradant blend

Family Cites Families (14)

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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
DE202780T1 (de) † 1985-04-25 1988-01-14 Allied Colloids Group Ltd., Bradford, Yorkshire Flockungsverfahren.
FR2589145A1 (fr) * 1985-10-25 1987-04-30 Snf Sa Agent floculant pour le traitement des boues a base de polymeres d'addition hydrosolubles ramifies
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
DE68921053T3 (de) * 1988-12-19 2004-07-22 Cytec Technology Corp., Wilmington Hochleistungs-Polymer-Flokkuliermittel.
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 (fr) * 1992-06-11 1994-12-02 Snf Sa Procédé de fabrication d'un papier ou d'un carton à rétention améliorée.
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 (fr) * 1995-10-30 1997-11-21 Snf Sa Procede pour ameliorer la retention dans un procede de fabrication du papier, carton et analogue
SE9504081D0 (sv) * 1995-11-15 1995-11-15 Eka Nobel Ab A process for the production of paper
JP3614609B2 (ja) * 1996-09-10 2005-01-26 ハイモ株式会社 製紙用薬剤、抄紙方法および製紙用薬剤の製造方法

Also Published As

Publication number Publication date
EP1092064B1 (fr) 2003-11-19
EP1092064B2 (fr) 2009-04-22
DE69912954D1 (de) 2003-12-24
ATE254693T1 (de) 2003-12-15
FR2779452B1 (fr) 2000-08-11
AU4043999A (en) 1999-12-20
CA2334196A1 (en) 1999-12-09
JP2002517626A (ja) 2002-06-18
KR20010052553A (ko) 2001-06-25
EP1092064A1 (fr) 2001-04-18
KR100685533B1 (ko) 2007-02-22
JP4699608B2 (ja) 2011-06-15
WO1999063159A1 (fr) 1999-12-09
CA2334196C (en) 2008-07-15
FR2779452A1 (fr) 1999-12-10
DE69912954T3 (de) 2010-01-28
DE69912954T2 (de) 2004-11-11

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