EP1282741B1 - Method of adsorption of cationic and anionic polymers on the surface of particles and paper or nonwoven product containing such particles - Google Patents

Method of adsorption of cationic and anionic polymers on the surface of particles and paper or nonwoven product containing such particles Download PDF

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Publication number
EP1282741B1
EP1282741B1 EP01916028A EP01916028A EP1282741B1 EP 1282741 B1 EP1282741 B1 EP 1282741B1 EP 01916028 A EP01916028 A EP 01916028A EP 01916028 A EP01916028 A EP 01916028A EP 1282741 B1 EP1282741 B1 EP 1282741B1
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EP
European Patent Office
Prior art keywords
particles
paper
particle
cationic
polymer
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Expired - Lifetime
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EP01916028A
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German (de)
English (en)
French (fr)
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EP1282741A1 (en
Inventor
Sussan Sandberg
Bo Andreasson
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Essity Hygiene and Health AB
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SCA Hygiene Products AB
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    • 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
    • D21H23/08—Controlling the addition by measuring pulp properties, e.g. zeta potential, pH
    • D21H23/10—Controlling the addition by measuring pulp properties, e.g. zeta potential, pH at least two kinds of compounds being added
    • 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
    • D21H21/14—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 characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D21H21/20—Wet strength agents
    • 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
    • D21H17/375—Poly(meth)acrylamide
    • 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides

Definitions

  • the present invention refers to a method of producing a particle or group of particles intended for use in paper- and/or nonwovenmaking having a coating of at least two, preferably at least three, outside each other located thin layers of cationic and anionic polymers, at which the particle or group of particles is treated in consecutive steps with solutions of the cationic and anionic polymers. It also refers to a paper or nonwoven product containing such particles or groups of particles and containing increased amounts of wet strength agent and to tissue paper having improved wet strength.
  • Dual surface treatment of filler particles with anionic and cationic polymers is disclosed in EP-A-0 850 879, WO-A-95/32335, US-A-4,495,245 and US-A-4,925,530. There is no indication that the treatment takes place under such controlled conditions that a double- or multilayer is created on the pulp fibers with the anionic component in one layer and the cationic component in the other layer.
  • EP-A-0 835 957 discloses the addition of a cationic wet strength agent to an aqueous fiber dispersion in a first step and then in a second step supplying an anionic wet strength agent to the aqueous fiber dispersion.
  • the wet charge of the aqueous fiber dispersion is then controlled within a specific range. This means that if the cationic wet strength agent has been added in excess also the anionic agent has to be added in excess in order to equalize the charge.
  • WO-A-99/45201 discloses a method for improving the efficiency of aqueous cationic wet strength additives by penetrating cellulose surfaces with reactive anionic compounds, thus providing the cellulose surface with additional anionic sites.
  • the object of the present invention is to provide a method according to above and which offers a way to ensure that each polymer for forming the respective layer on the surface of the particles or group of particles is added only in such an amount in each step that substantially all polymer is adsorbed to the particle surface.
  • the Z-potential of the particles or groups of particles may be measured.
  • the particles or groups of particles may be of optional type, however fibers, e g cellulosic fibers, regenerated fibers and different types of synthetic fibers, and filler particles are mainly concerned.
  • the interacting polymers are preferably alternating cationic and anionic polyelectrolytes, but they may also be so called zwitter ions.
  • the particles are cellulose fibers for papermaking and at least one of the polymers is a strength additive such as a wet and/or dry strength agent.
  • the invention also refers to a paper or nonwoven product, which contains fibers and/or filler particles having at least three outside each other located thin layers of alternating cationic and anionic polymers and containing increased amounts of wet strength agent.
  • the term paper used herein refers to all types of paper, such as tissue paper, graphical paper, linerboard, wiping material etc.
  • the nonwoven material could be of optional type.
  • the invention further refers to tissue paper having improved wet strength.
  • particles or groups of particles are treated with alternating cationic and anionic polymers in order to build up thin multilayers of the interacting polymers on the particle surface.
  • the particles are treated in consecutive steps with solutions of the alternating cationic and anionic polymers, at which the treatment time for each step is sufficient for forming a layer of the desired molecular thickness.
  • the first layer should be a cationic polymer, and vice versa.
  • the addition is controlled in such a way that substantially no excess amount of the respective polymer is added in each step, so that substantially all polymer is adsorbed to the particle surface.
  • This is made by measuring the electric charge of the treatment solution or the liquid in which the treated particles or groups of particles are contained. After having allowed the polymer to adsorb to the particle surface a certain period of time the electric charge of the solution should be close to zero.
  • the charge measurements are made with streaming potential measurement, e g with a PCD instrument (Particle Charge Detector).
  • the Z-potential is measured according to the method described below.
  • the method according to the invention for building the desired multilayers is based on electrostatic attraction between oppositely charged polyelectrolytes. By treating the particles in consecutive steps with a solution containing polyions of opposite charge and permit these spontaneously to adsorb to the particle surface, multilayers of the stated kind are built up. In principle all types of polyelectrolytes may be used.
  • the method is used for adsorbing strength additives to cellulosic fibers used for papermaking.
  • the first polymer to be adsorbed is a cationic polymer.
  • This layer will make the fibre surface cationically charged.
  • an anionic polymer e g CMC (carboxy methyl cellulose)
  • the fiber surface will then turn anionic again.
  • the next layer of cationic polymer can be added and so on.
  • ion-exchanging fibers where "membranes" with ion-exchanging properties are provided on the fiber surface, wet strength agents where the added polymers are reactive with the fibers and with each other, in order to provide permanent bonds between the fibers and for the production of highly swelling surface layers, where the added chemicals form swollen gel structures on the fiber surface for use in absorbent hygiene products.
  • Another possible application are new types of fibers for printing paper, where the adsorbed polymers change colour when they are exerted to an electric, magnetic or electromagnetic field. Such polymers are available today.
  • the fibers that are treated with the method according to the invention can be of optional kind, natural as well as synthetic fibers. Mainly cellulosic fiber are concerned. However it would be possible to treat synthetic fibers, for example for giving them a more hydrophilic surface.
  • Anionic polyelectrolytes Anionic starch with different degrees of substitution, anionic guar, polystyrene sulfonate, carboxy methyl cellulose with different degrees of substitution, anionic galactoglucomannan, polyphosphoric acid, polymethacrylic acid, polyvinyl sulphate, alginate, copolymers of acryl amide and acrylic acid or 2-acrylic amide-2-alkylpropane sulphonic acid.
  • Cationic polyelectrolyte Cationic galactoglucomannan, cationic guar, cationic starch, polyvinyl amine, polyvinyl pyridine and its N-alkyl derivatives, polyvinyl pyrrolidone, chitosan, alginate, modified polyacryl amides, polydiallyl dialkyl, cationic amide amines, condensation products between dicyane diamides, formaldehyde and an ammonium salt, reaction products between epichlorhydrine, polyepichlorhydrine and ammonia, primary and secondary amines, polymers formed by reaction between ditertiary amines or secondary amines or dihaloalkanes, polyethylene imines and polymers formed by polymerisation of -(dialkylaminoalkyl)acrylic amide monomers.
  • the PAE and G-PAM was diluted in deionized water to an active content of 10 g/l before use.
  • the different CMC's were dissolved in deionized water by dispersion using a hand mixer, to a suitable concentration between 5 and 10 g/l depending on the viscosity.
  • the pulp used was a dried fully bleached TCF, Celeste 85, from SCA ⁇ strand.
  • the pulp was beaten to 25°SR and was diluted with tap water to a concentration of 3 g/l.
  • the pH during the trials was 7.5 and the conductivity was set to 1200 ⁇ S/cm using NaCl.
  • Adsorption time for the additives were 10 minutes.
  • the Z-potential of the fibres was measured with a streaming potential instrument (Magendans SZ2, supplied by Mütek) [Penniman, J.G., Comparison of pulp pad streaming potential measurement and mobility measurement. Tappi Journal, 1992 75 111-115 and Jaycock, M.J.; Assumptions made in the measurement of zeta-potential by streaming current / potential detectors . Paper Technology, 1995 36 35-38.19, 20; Barron, W., et al ., The streaming current detector: a comparison with conventional electrokinetic techniques. Colloids and Surfaces, 1994 88 129-139; Sanders, N.D. and J.H. Schaefer, Comparing papermaking wet-end charge-measuring techniques in kraft and groundwood systems .
  • Magendans SZ2 supplied by Mütek
  • a PCD 03 Particle Charge Detector supplied by Mütek measures a voltage difference induced by a moving charged medium, e.g. colloidal substances in a white water. High molecular mass polymers and colloidal substances attach to the Teflon surfaces of the equipment. The oscillating piston moves and induces a potential difference that is detected [Jaycock, M.J., Assumptions made in the measurement of zeta-potential by streaming current / potential detectors. Paper Technology, 1995 36 35-38 ; Barron, W., et al., The streaming current detector: a comparison with conventional electrokinetic techniques. Colloids and Surfaces, 1994 88 129-139 and Sanders, N.D. and J.H.
  • PAE and G-PAM adsorption in the sheets was analysed by measuring the total nitrogen content in the sheets.
  • the method is based on flash combustion and is called Dumas Total Nitrogen Analysis and the measuring instrument used is Carlo Erba Instrument NA 1500 supplied by CE Termo Quest. A manual is supplied together with the instrument.
  • PAE and G-PAM adsorption in the sheets was analysed by ion exclusion chromatography.
  • 1 g of paper sample is hydrolysed with 1.0 M NaOH. The hydrolysis is done at 100°C for 24 hours.
  • the PAAE resin is then hydrolysed to DETA and Adipate (see formula below).
  • the solution is neutralised with an ion exchanger and the resulting adipic acid is analysed with ion exclusion chromatography.
  • the wet strength resin is treated and analysed in the same way to calculate the amount of adipic acid in the actual resin. This result is then used to calculate the amount of PAE resin in paper.
  • Ion exclusion chromatography is mainly used for analysis of weak inorganic and organic acids.
  • the chromatographic column is packed with a stationary phase consisting of a sulfonated polystyrene/divinylbensene based cation exchanger.
  • a stationary phase consisting of a sulfonated polystyrene/divinylbensene based cation exchanger.
  • different organic acids may diffuse into the stationary phase to a greater or lesser degree.
  • This mechanism together with ion exchange is used for chromatographic separation of organic acids in solution. Suppressed conductivity is used for detection.
  • the working range for the method is 0.01- 1.0 % in paper (calculated as dry PAE resin) and the relative standard deviation for a paper sample with 0.3 % PAE (dry resin) is 3.8 %.
  • Fig. 1 shows the Z-potential of the fibres during trial 1, before and after washing of the fibres.
  • the Z-potential is not largely influenced by washing the fibres.
  • a small decrease in the observed Z-potential can be detected when washing the PAE treated fibres and a small increase when washing the CMC treated fibres, which presumedly is due to the additive desorption during the washing step.
  • Fig. 2 shows the results of charge measurements of the colloidal phase (PCD measurements) during trial 1, before and after washing of the fibres.
  • Fig. 2 shows that when adding PAE / CMC in excess a large amount of the added polymer stays in the colloidal phase instead of adsorbing to the fibres. In the washing step the excess is removed.
  • Fig. 3 shows the wet tensile index of the sheets versus the adsorbed amount of PAE.
  • Dry tensile strength index show a similar trend as the wet tensile strength index but, as expected, the increase in dry strength is not as high as the increase in wet strength.
  • the charge in the colloidal phase is balancing around zero charge, indicating that the adsorption of PAE / CMC on the fibres is almost total, i e not much of the additives end up in the water phase.
  • the deviation from zero charge should preferably not exceed ⁇ 5 ⁇ eq/l, more preferably not exceed ⁇ 2 ⁇ eq/l.
  • Fig. 6 there is shown the dry tensile strength index versus adsorbed amount of PAE, at which e g "7/2/7-10-15" means 7 mg/g PAE, 2 mg/g CMC, then 7, 10, 15 mg/g PAE in the third layer.
  • the dry tensile strength index reached its highest level at relatively low adsorbed amounts of PAE. At an adsorbed amount of approximately 5 mg/g the strength is levelling out.
  • Fig. 7 there is shown the wet tensile strength index versus adsorbed amount of PAE.
  • Fig. 8 shows the relative wet strength versus adsorbed amount of PAE.
  • Fig. 7 and 8 show that wet tensile strength index and the relative wet strength level out, but it seems like the highest level is not fully reached.
  • the dry tensile index start to level out at 5 mg/g adsorbed amount of PAE.
  • the wet tensile strength index levels out but at higher levels of adsorbed amount of PAE.
  • a maximum relative wet strength of 40% is reached.
  • the trials show that charge measurements using PCD and Z-potential instruments provide good control of polymer addition.
  • the multilayering technique gives an increased amount of additives that are adsorbed to the fibres, which helps to give e g an increased strength up to a certain level.
  • the amount of polymer to be added is preferably controlled and determined by Z-potential and PCD measurements after each addition of polymer in each step during the starting up of the process. These amounts are then used in the process.
  • the Z-potential and PCD measurements are during the run of the process preferably performed only after the headbox. Addition of the first polymer is e g made in the pulper, and the other polymers are then added at different steps in the wet end of the paper machine.
  • wet strength agents such as PAE and G-PAM it is possible by the method according to the invention to produce paper and nonwoven products containing at least 1.5, preferably at least 1.7, more preferably at least 2.0, even more preferably at least 2.2 and most preferably at least 2.5 % by weight or more of a wet-strength agent.
  • wet strength agents such as PAE and G-PAM
  • these values refer to the amount of wet-strength agent adhering to the fibres and measured according to the total nitrogen method disclosed above. In some of the laboratory trials up to 3.8 % by weight wet-strength agent adhered to the fibres (Fig. 7 and 8).
  • tissue paper based on cellulose fibres with no admixture of other types of fibres, such as synthetic reinforcing fibres, having a wet tensile index of at least 6.5, preferably at least 7.0 and more preferably at least 7.5 Nm/g.
  • tissue paper in this respect does not include materials exerted to hydroentangling.
  • No. 1 is a tissue paper used as wiping material sold by SCA Hygiene Products AB under the trademark "M-Tork” and having the following pulp composition: 33% by weight CTMP and 67% by weight softwood kraft pulp (TCF). It contains about 0.7% by weight PAE.
  • No. 2 is a paper produced from the same type of pulps as No. 1 and where the cellulose fibres were treated in consecutive steps according to the invention with two layers PAE, one layer G-PAM and two layers CMC. It is from these results seen that tissue paper no. 2 showed improved strength properties. It is further noted that the papers tested contained a mixture of CTMP and softwood kraft pulp.
  • Sample 1 (ref.) 2 (invention) Grammage g/m 2 24 21 Thickness 2kPa ⁇ m 154 162 Bulk 2kPa cm 3 /g 6.4 7.7
  • Tensile strength MD, dry N/m 242 438 Tensile strength CD, dry N/m 223 340
  • Tensile strength MD, water N/m 102.9 206.8 Tensile strength CD, water N/m 60.8 125.8
  • Table 4 shows the results of measurements for determining the amount of wet strength agent in the form of PAE in some commercially available tissue products and in a tissue paper made with the method according to the invention.
  • Sample A is a tissue paper made according to the invention corresponding to the one tested as No. 2 in Table 3.
  • Sample B is a tissue paper produced by Fort James and sold under the trade name "Lotus Profes”.
  • Sample C is a tissue paper produced by Procter & Gamble and sold under the trade name “Bounty”.
  • Sample D is a tissue paper produced by Metsä Särla and sold under the trade name "Katrin Cleany”.
  • the amount of PAE in the different tissue papers were measured by the ion exclusion chromatography method described above and gives the amount of PAE adsorbed to the fibres. It is to be noted that normally the amount of PAE or other wet strength agent added to the furnish is given as % of the wet strength agent solution added per weight fibres. Wet strength agents are sold as solutions containing between about 6 and 25 % of the active component. When we talk about the amount of wet strength agent we refer to the amount of the active component adhered to the fibres. Sample A (invention) B (ref.) C (ref.) D (ref.) Amount PAE (% by weight) 2 0.45 1.2 0.7

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EP01916028A 2000-04-06 2001-03-22 Method of adsorption of cationic and anionic polymers on the surface of particles and paper or nonwoven product containing such particles Expired - Lifetime EP1282741B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE0001268A SE0001268L (sv) 2000-04-06 2000-04-06 Förfarande för adsorption av på varandra följande tunna skikt av katjoniska och anjoniska polymerer på ytan hos partiklar eller grupper av partiklar, och pappers- eller nonwovenprodukt innehållande s ådana partiklar eller grupper av partiklar
SE0001268 2000-04-06
PCT/SE2001/000612 WO2001077437A1 (en) 2000-04-06 2001-03-22 Method of adsorption of cationic and anionic polymers on the surface of particles and paper or nonwoven product containing such particles

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EP1282741A1 EP1282741A1 (en) 2003-02-12
EP1282741B1 true EP1282741B1 (en) 2004-02-18

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EP (1) EP1282741B1 (sv)
CN (1) CN1422347A (sv)
AT (1) ATE259917T1 (sv)
AU (1) AU2001242971A1 (sv)
BR (1) BR0109841A (sv)
DE (1) DE60102082T2 (sv)
ES (1) ES2215887T3 (sv)
HU (1) HUP0300410A2 (sv)
MX (1) MXPA02009106A (sv)
PL (1) PL357809A1 (sv)
RU (1) RU2002129503A (sv)
SE (1) SE0001268L (sv)
SK (1) SK14682002A3 (sv)
WO (1) WO2001077437A1 (sv)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102242524A (zh) * 2011-06-24 2011-11-16 浙江理工大学 一种构建纳米聚电解质多层膜改善废纸纤维强度的方法
US8163134B2 (en) 2008-09-22 2012-04-24 Hercules Incorporated Copolymer blend compositions for use to increase paper filler content

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6755938B2 (en) 2001-08-20 2004-06-29 Armstrong World Industries, Inc. Fibrous sheet binders
US6824650B2 (en) † 2001-12-18 2004-11-30 Kimberly-Clark Worldwide, Inc. Fibrous materials treated with a polyvinylamine polymer
US6723204B2 (en) * 2002-04-08 2004-04-20 Hercules Incorporated Process for increasing the dry strength of paper
US6939443B2 (en) * 2002-06-19 2005-09-06 Lanxess Corporation Anionic functional promoter and charge control agent
US7041197B2 (en) 2003-04-15 2006-05-09 Fort James Corporation Wet strength and softness enhancement of paper products
US7696401B2 (en) 2003-07-31 2010-04-13 Evonik Stockhausen, Inc. Absorbent materials and absorbent articles incorporating such absorbent materials
WO2006041401A1 (en) * 2004-10-15 2006-04-20 Stora Enso Ab Process for producing a paper or board and a paper or board produced according to the process
EP4202119A1 (en) * 2021-12-22 2023-06-28 Billerud Aktiebolag (publ) Reclable paper of high wet strength

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Publication number Priority date Publication date Assignee Title
DE69314202T2 (de) * 1992-03-12 1998-05-14 Oji Paper Co Verfahren zur Herstellung eines Wischvliesstoffs
IL113721A (en) * 1994-05-20 1999-04-11 Minerals Tech Inc Dual surface treated filler material method for its preparation and use in papermaking
US5783041A (en) * 1996-04-18 1998-07-21 Callaway Corporation Method for imparting strength to paper
US6419789B1 (en) * 1996-10-11 2002-07-16 Fort James Corporation Method of making a non compacted paper web containing refined long fiber using a charge controlled headbox and a single ply towel made by the process
US5935383A (en) * 1996-12-04 1999-08-10 Kimberly-Clark Worldwide, Inc. Method for improved wet strength paper
SE521591C2 (sv) * 1998-11-30 2003-11-18 Sca Res Ab Metod att framställa en partikel uppvisande beläggning av med varandra växelverkande polymerer och pappers -eller nonwovenprodukt innehållande partiklarna

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8163134B2 (en) 2008-09-22 2012-04-24 Hercules Incorporated Copolymer blend compositions for use to increase paper filler content
CN102242524A (zh) * 2011-06-24 2011-11-16 浙江理工大学 一种构建纳米聚电解质多层膜改善废纸纤维强度的方法
CN102242524B (zh) * 2011-06-24 2013-06-26 浙江理工大学 一种构建纳米聚电解质多层膜改善废纸纤维强度的方法

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SE0001268L (sv) 2001-10-07
PL357809A1 (en) 2004-07-26
CN1422347A (zh) 2003-06-04
DE60102082D1 (de) 2004-03-25
WO2001077437A1 (en) 2001-10-18
RU2002129503A (ru) 2004-03-27
SE0001268D0 (sv) 2000-04-06
AU2001242971A1 (en) 2001-10-23
DE60102082T2 (de) 2004-12-23
BR0109841A (pt) 2003-06-03
EP1282741A1 (en) 2003-02-12
SK14682002A3 (sk) 2003-04-01
MXPA02009106A (es) 2003-03-12
ES2215887T3 (es) 2004-10-16
ATE259917T1 (de) 2004-03-15
HUP0300410A2 (en) 2003-06-28

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