US20040256067A1 - Filler for the manufacture of base paper and method for the manufacture of base paper - Google Patents

Filler for the manufacture of base paper and method for the manufacture of base paper Download PDF

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Publication number
US20040256067A1
US20040256067A1 US10/496,123 US49612304A US2004256067A1 US 20040256067 A1 US20040256067 A1 US 20040256067A1 US 49612304 A US49612304 A US 49612304A US 2004256067 A1 US2004256067 A1 US 2004256067A1
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US
United States
Prior art keywords
hardwood pulp
pulp
aspen
mechanical
base paper
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.)
Abandoned
Application number
US10/496,123
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English (en)
Inventor
Markku Leskela
Stina Nygard
Gudrun Pauler-Johansson
Maija Pitakanen
Eeva Anas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Metsa Board Oyj
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Individual
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
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Assigned to M-REAL OYJ reassignment M-REAL OYJ ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ANAS, EEVA, PITKANEN, MAIJA, LESKELA, MARKKU, NYGARD, STINA, PAULER-JOHANSSON, GUDRUN
Publication of US20040256067A1 publication Critical patent/US20040256067A1/en
Abandoned legal-status Critical Current

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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
    • 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
    • D21H17/675—Oxides, hydroxides or carbonates
    • 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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/02—Chemical or chemomechanical or chemothermomechanical 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
    • 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
    • D21H21/50—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 form
    • D21H21/52—Additives of definite length or shape

Definitions

  • the present invention relates to the use of precipitated calcium carbonates (PCC) as fillers for the manufacture of base paper together with mechanical hardwood pulp and chemical softwood pulp, and to a method for the manufacture of base paper, in which method pulp produced from hard woods, in particular from the wood of the genus Populus , and chemical softwood pulp are used together with a PCC filler.
  • PCC precipitated calcium carbonates
  • base papers in particular in thin base papers, kaolins and ground calcium carbonates (GCC) are used as fillers.
  • GCC ground calcium carbonates
  • Thin base papers are traditionally manufactured in acidic conditions, wherein it is not possible to use calcium carbonates but other compounds, and thus PCC and GCC are used mainly in fine papers.
  • the paper In coated base papers, the paper must be dense in order that coating colour shall stay on the surface of the paper forming a well-covering layer and shall not be able to penetrate into the base paper during the coating process. In order that coated paper should have good printability, it is desired that coating layers cover the base paper completely. Thin coating layers shall provide good coverage and the gloss of printed paper shall be high without disturbing variation. Moreover, the bonding strength of the paper, which is measured, when needed, as a Scott bond value, must be sufficiently high in order that the paper shall not crack during printing.
  • Papers are printed typically with a heatset offset printing press, in which connection the surface of finished coated paper may bubble if the strength of the base paper in the z-direction is not sufficient. This phenomenon is particularly critical in the case of double-coated paper when the surface of the paper is dense and the vapours produced from the paper's own moisture in the dryer section of the heat offset printing press cannot escape through the surfaces of the paper.
  • the filler should additionally have a high opacity (light scattering) and brightness, but at the same time it is also very important that the filler does not reduce the bonding strength of the paper nor, on the other hand, increase the porosity of the base paper.
  • PCC precipitated calcium carbonates
  • the advantages attained are basically based on the fact that in the process of manufacturing PCC the shape and size of particles can be controlled by varying process control parameters. High brightness is based on the fact that, since the process is synthetic, by means of pure raw materials it is possible to obtain an end result that is better than that of ground calcium carbonates. The manufacture of PCC is also economically competitive in large plants as compared with other fillers.
  • Calcium carbonate pigments can generally be used only in papermaking processes that have a neutral or alkaline pH. Carbonates dissolve under acidic conditions. It has been possible to avoid this limitation as well by developing PCC pigments that can be used in slightly acidic conditions.
  • PCC pigments have achieved a strong position as fillers of uncoated fine papers, the particles being typically complex in shape and fairly large in size, and also in coatings of fine papers, the particles being typically simpler and smaller in size.
  • PCC fillers are used in uncoated office papers in proportions of over 15 wt-%, the aim being to increase brightness and opacity and to reduce costs.
  • the particle morphology of PCC has been designed so that bulk is also preserved as well as possible.
  • the particles of PCC are “sea urchin”-like in morphology, which is again very weak from the viewpoint of the density and bonding strength of the web.
  • Synthetic precipitated PCC is either aragonite or calcite depending on the manufacturing conditions. Typically, aragonite is needle-like in morphology, which is suitable for the coating of paper. Calcite precipitates as scalenohedral, i.e.
  • FIG. 1 illustrates the particles by means of SEM pictures.
  • the particles used in the coatings of fine papers are simpler in type and smaller in size.
  • the PCC pigments have not achieved any particular success as fillers of thin base papers.
  • the filler shall have high brightness and opacity, i.e. light-scattering, but at the same time it is very important that the fillers do not lower the bonding strength of the paper and, on the other hand, do not increase the porosity of the base paper.
  • opacity decreases, which, in turn, must be compensated for by increasing the light-scattering coefficient.
  • density naturally deteriorates, i.e. decreases when the basis weight is reduced.
  • PCC fillers do not meet simultaneously all the requirements associated with the manufacture of thin base paper.
  • the brightness and opacity of the base paper may be high but, at the same time, the bonding strength of the base paper has decreased to an alarming extent and its density has deteriorated such that the coating colour has penetrated into the base paper.
  • FI patent 100 729 describes a filler used in paper manufacture and mainly consisting of calcium carbonate, and a method for its manufacture.
  • calcium carbonate is precipitated onto the surface of noil fibrils produced from cellulose fibre and/or mechanical pulp fibre by refining.
  • This filler that is based on cellulose fibre or mechanical pulp fibre and on calcium carbonate imparts good optical properties and good strength to the paper.
  • FI patent 103 417 discloses a method for manufacturing a base paper suitable for the manufacture of coated fine paper by combining groundwood pulp made from hardwood and chemical softwood pulp.
  • mechanical pulp manufactured from aspen or from wood of the genus Populus and chemical softwood pulp are used as a combination, thereby producing a pulp suitable for the manufacture of base paper in respect of its strength properties.
  • the advantages of aspen pulp include high brightness and brightness stability as compared with spruce groundwood. This is due in particular to the low lignin content of aspen groundwood pulp or equivalent mechanical pulp and to its low concentration of carbonyl groups. By this means it is possible to manufacture fine paper with high brightness with a lower basis weight than usual.
  • PCC type filler which is suitable in particular for the manufacture of thin base paper together with mechanical hardwood pulp and chemical softwood pulp and which meets simultaneously all the requirements placed on the filler of base paper, as well as for a method for the manufacture of a base paper in which mechanical pulp based on hard woods, such as aspen or trees of the genus Populus , and chemical softwood pulp are used together with a PCC filler.
  • An object of the invention is to provide a method for the manufacture of base paper, in particular for the manufacture of thin base paper, by means of which a base paper is obtained that has a low basis weight, a good internal strength and density, as well as improved light-scattering and opacity.
  • An object of the invention is also the use of precipitated calcium carbonate (PCC) as a filler for the manufacture of base paper together with mechanical hardwood pulp and chemical softwood pulp, which filler meets in particular the requirements placed above on the filler of base paper.
  • PCC precipitated calcium carbonate
  • An object of the invention is further to provide a method for the manufacture of base paper, in which method mechanical pulp based on hard woods, such as aspen or trees of the genus Populus , and chemical softwood pulp are used together with a PCC filler, whereby all the desired properties of the base paper can be achieved simultaneously.
  • mechanical hardwood pulp which is advantageously produced from aspen or from hard woods of the genus Populus , i.e. wood species of the genus Populus , which are preferably selected from the group of the following species: P. tremula, P. tremuloides, P. balsamea, P. balsamifera, P. trichocarpa and P. heterophylla , or aspen species crossbred from different mother aspens, such as hybrid aspen species, and species produced by gene technology, or poplar, or from a blend of mechanical pulps produced from the above-mentioned species.
  • Particularly preferable wood species are native aspen P. tremula , Canadian aspen P. tremuloides , poplar and hybrid aspen.
  • Mechanical hardwood pulp may optionally contain 70 wt-% of spruce or pine at the maximum.
  • Such mechanical hardwood pulps can be prepared as blends that contain, for example, two hard woods and then, for example, spruce, as softwood.
  • the proportion of spruce may be 70% at the maximum, preferably 50% at the maximum, and particularly preferably below 30%.
  • Mechanical hardwood pulps have shorter fibres than chemical birch pulp or mechanical spruce pulps. Therefore the same basis weight of mechanical hardwood pulp comprises more fibres than chemical birch pulp or mechanical spruce pulp. This results in a higher light-scattering ability, a good formation, i.e. a lower variation of basis weight in a small scale, in a low surface roughness, and bulk is also good.
  • CMTP chemimechanical pulp
  • PGW pressure groundwood
  • 20-70 wt-% of mechanical hardwood pulp preferably aspen-CTMP or aspen-PGW or a combination of them, and 80-30 wt-% of bleached chemical softwood pulp, calculating from the dry solids of stock, are used, and at least 20% of the fibres of the mechanical hardwood pulp are included in the fibre size fraction of ⁇ 200 mesh and preferably 10-40 wt-% of them are included in the fibre size fraction of ⁇ fraction (28/48) ⁇ mesh.
  • at least 30 wt-% and particularly preferably at least 50 wt-% of the fibres of the hardwood pulp originate from aspen, hybrid aspen and/or poplar.
  • Hardwood raw material is chipped, after which mechanical pulp, refiner mechanical pulp (TMP) or chemimechanical pulp (CTMP) is manufactured from the chips in a manner known in itself
  • TMP refiner mechanical pulp
  • CMP chemimechanical pulp
  • a stock is prepared from the mechanical pulp together with chemical pulp, and a PCC filler having a particle size distribution of 90% ⁇ 9 ⁇ m, 50% ⁇ 5 ⁇ m and 20% ⁇ 1.5 ⁇ m is used as a filler.
  • the stock may contain additives, such as different starches, starch derivatives and retention agents.
  • the dry solids content of the stock is 0.1-5 wt-%.
  • the water phase of the stock it is possible to use, for example, the circulation water of the paper machine.
  • Bleached chemical softwood pulp is preferably used as the chemical pulp.
  • the amount of the mechanical pulp is then 20-80 wt-%, preferably 30-70 wt-% and the amount of the bleached chemical softwood pulp is 80-20 wt-%, preferably 70-30 wt-%, calculated from the dry solids of the stock.
  • a paper web is formed for a paper machine from the stock of mechanical hardwood pulp and chemical pulp in accordance with the prior art, for example, by using a gap former.
  • basis weight 25-150 g/m 2 , preferably 25-80 g/m 2 ,
  • bonding strength ⁇ 200, preferably ⁇ 250 and very preferably ⁇ 300
  • porosity of paper preferably ⁇ 300 ml/min and very preferably ⁇ 250 ml/min (in basis weight of 50 g/m 2 ),
  • the fibre composition of the base paper in accordance with the invention comprises 20-70 wt-% of mechanical hardwood pulp, preferably aspen-based pulp, most preferably aspen groundwood or aspen-CTMP pulp and very preferably aspen-CTMP pulp, and 80-30 wt-% of chemical softwood pulp, preferably bleached chemical pine pulp.
  • the base paper can be coated by any suitable method known in the art, whereby a coating layer having a basis weight of 5-50 g/m 2 , preferably 5-30 g/m 2 , is formed on at least one surface, preferably on both surfaces of the paper web.
  • High-quality fine paper is obtained from the base paper in accordance with the invention by coating it with a suitable pigment-containing coating colour.
  • the coating colour can be applied to the material web in a manner known in itself.
  • the coating of the paper can be carried out on-line or off-line by means of a conventional coating device, i.e. by blade coating, or by means of film coating or surface spraying.
  • the base paper manufactured by the method in accordance with the invention and the coated paper manufactured further from it can be calendered by any calendering method known in the prior art.
  • calendering is accomplished on-line as soft calendering, thereby obtaining smooth and glossy or matte-surfaced products whose bulk, opacity and stiffness meet the requirements.
  • McNett classification ⁇ fraction (100/200) ⁇ mesh 11.0%
  • tear index 3.4 mNm 2 /g
  • filler of base paper is composed both of so-called fresh filler and of the filler coming from coated paper broke (the filler containing the mineral pigments of coating layer). For this reason, the filler was dosed to some of the test points as coated broke from a paper mill, in which broke the mineral main component was the ground carbonate contained in the coating. At these points, fresh filler constituted 6 percentage units of the filler and the filler coming from broke constituted 6 percentage units thereof.
  • FIG. 2 illustrates the particle size distributions graphically. The values have been measured on a Malvern Master Size device. TABLE 1 Particle size Area Filler D50, ⁇ m m 2 /g GCC1, ground calcium carbonate 1.67 6.64 GCC2, ground calcium carbonate 1.1 7.77 PCC1, scalenohedral 2.6 4.98 PCC2, rhombohedral 1.4 7.58 PCC3, scalenohedral/prismatic blend 3.6 3.77
  • McNett classification ⁇ fraction (50/200) ⁇ mesh 34.1%
  • PCC2 rhombohedral
  • the base papers were coated with the same coating colours and supercalendered.
  • the target coating amount was 18 g/m 2 on both sides of paper.
  • the lineal pressure of calendering was 280 kN/m.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
US10/496,123 2001-11-28 2002-11-21 Filler for the manufacture of base paper and method for the manufacture of base paper Abandoned US20040256067A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI20012328A FI116573B (sv) 2001-11-28 2001-11-28 Fyllnadsämne för framställning av tunn baspapper och förfarande för framställning av baspapper
FI20012328 2001-11-28
PCT/FI2002/000939 WO2003050355A1 (en) 2001-11-28 2002-11-21 Filler for the manufacture of base paper and method for the manufacture of base paper

Publications (1)

Publication Number Publication Date
US20040256067A1 true US20040256067A1 (en) 2004-12-23

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US10/496,123 Abandoned US20040256067A1 (en) 2001-11-28 2002-11-21 Filler for the manufacture of base paper and method for the manufacture of base paper

Country Status (9)

Country Link
US (1) US20040256067A1 (sv)
EP (1) EP1458929A1 (sv)
JP (1) JP2005511916A (sv)
CN (1) CN1309904C (sv)
AU (1) AU2002366533B2 (sv)
CA (1) CA2466899A1 (sv)
FI (1) FI116573B (sv)
NZ (1) NZ533042A (sv)
WO (1) WO2003050355A1 (sv)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060060318A1 (en) * 2002-10-24 2006-03-23 Petri Silenius Method for manufacturing paper and board
US20080006380A1 (en) * 2006-05-19 2008-01-10 Abitibi-Consolidated, Inc. Coated Mechanical Pulp Paper
US20080041275A1 (en) * 2006-08-17 2008-02-21 Colin Wayne Hansen UV varnish gloss performance using novel pigment and process for making same
US9068292B2 (en) 2013-01-30 2015-06-30 Hewlett-Packard Development Company, L.P. Uncoated recording media
US9435079B2 (en) 2012-05-25 2016-09-06 Hewlett-Packard Development Company, L.P. Uncoated recording media

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101031686A (zh) * 2004-07-14 2007-09-05 国际纸业公司 造纸方法
CN1303286C (zh) * 2005-06-20 2007-03-07 上海东升新材料有限公司 碳酸钙的包覆的纸浆纤维及其制备方法和在造纸中的应用
JP2008248417A (ja) * 2007-03-29 2008-10-16 Nippon Paper Industries Co Ltd 広葉樹機械パルプ
ES2526757T3 (es) 2008-09-09 2015-01-15 Omya International Ag Composiciones de carbonatos cálcicos/pigmentos para formulaciones de papel, que muestran reducción del traspaso de impresión
JP5462572B2 (ja) * 2008-09-30 2014-04-02 日本製紙株式会社 印刷用塗工紙およびその製造方法
JP5462570B2 (ja) * 2008-09-30 2014-04-02 日本製紙株式会社 グラビア印刷用塗工紙およびその製造方法
JP5893795B2 (ja) * 2012-03-23 2016-03-23 オムヤ インターナショナル アーゲー 偏三角面体状の沈降炭酸カルシウムを調製するための方法
JP6077360B2 (ja) * 2012-03-30 2017-02-08 日本製紙株式会社 紙の製造方法
SE539437C2 (sv) * 2015-03-31 2017-09-19 Stora Enso Oyj A method of producing filler from fractionated fly ash
CN107663805B (zh) * 2017-10-11 2020-10-30 山东恒安纸业有限公司 一种无菌擦手纸及其生产工艺
CN111021126B (zh) * 2019-12-27 2022-06-07 民丰特种纸股份有限公司 一种低定量离型原纸及其制备方法

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US4335184A (en) * 1979-10-15 1982-06-15 Mitsubishi Paper Mills, Ltd. Recording paper
US4732748A (en) * 1986-12-10 1988-03-22 Cyprus Mines Corporation Finely divided calcium carbonate compositions
US5262006A (en) * 1989-02-13 1993-11-16 Mo Och Domsjo Aktibolag Paper manufacturing process, and papers obtainable by means of that process
US5653795A (en) * 1995-11-16 1997-08-05 Columbia River Carbonates Bulking and opacifying fillers for cellulosic products
US5662995A (en) * 1994-07-04 1997-09-02 Fuji Xerox Co., Ltd. Transfer paper for electrophotography and process for producing the same
US5695610A (en) * 1993-10-15 1997-12-09 Basf Aktiengesellschaft Aqueous pigment slurries and their use in the production of filler-containing paper
US5939036A (en) * 1997-04-21 1999-08-17 Goldcorp Inc. Manufacture of precipitated calcium carbonate
US6036933A (en) * 1995-03-02 2000-03-14 Pretoria Portland Cement Company Limited Calcium carbonate precipitation method
US6143065A (en) * 1999-07-12 2000-11-07 J. M. Huber Corporation Precipitated calcium carbonate product having improved brightness and method of preparing the same
US6251222B1 (en) * 1995-06-29 2001-06-26 Metsa-Serla Filler for use in paper manufacture and procedure for producing a filler
US6391154B1 (en) * 1997-09-16 2002-05-21 M-Real Oyj Paper web and a method for the production thereof

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
US6228161B1 (en) * 1996-12-30 2001-05-08 Minerals Technologies Inc. Use of calcium carbonate in an acidic aqueous media
FI104502B (sv) * 1997-09-16 2000-02-15 Metsae Serla Oyj Förfarande för framställning av pappersbana
AU4030199A (en) * 1998-05-27 1999-12-13 J.M. Huber Denmark Aps Use of colloidal precipitated calcium carbonate as a filter in the preparation of paper
FI111401B (sv) * 2000-01-28 2003-07-15 M Real Oyj Förfarande för framställning av en kalandrerad pappersbana samt en kalandrerad pappersprodukt

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4335184A (en) * 1979-10-15 1982-06-15 Mitsubishi Paper Mills, Ltd. Recording paper
US4732748A (en) * 1986-12-10 1988-03-22 Cyprus Mines Corporation Finely divided calcium carbonate compositions
US5262006A (en) * 1989-02-13 1993-11-16 Mo Och Domsjo Aktibolag Paper manufacturing process, and papers obtainable by means of that process
US5695610A (en) * 1993-10-15 1997-12-09 Basf Aktiengesellschaft Aqueous pigment slurries and their use in the production of filler-containing paper
US5662995A (en) * 1994-07-04 1997-09-02 Fuji Xerox Co., Ltd. Transfer paper for electrophotography and process for producing the same
US6036933A (en) * 1995-03-02 2000-03-14 Pretoria Portland Cement Company Limited Calcium carbonate precipitation method
US6251222B1 (en) * 1995-06-29 2001-06-26 Metsa-Serla Filler for use in paper manufacture and procedure for producing a filler
US5653795A (en) * 1995-11-16 1997-08-05 Columbia River Carbonates Bulking and opacifying fillers for cellulosic products
US5939036A (en) * 1997-04-21 1999-08-17 Goldcorp Inc. Manufacture of precipitated calcium carbonate
US6391154B1 (en) * 1997-09-16 2002-05-21 M-Real Oyj Paper web and a method for the production thereof
US6143065A (en) * 1999-07-12 2000-11-07 J. M. Huber Corporation Precipitated calcium carbonate product having improved brightness and method of preparing the same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060060318A1 (en) * 2002-10-24 2006-03-23 Petri Silenius Method for manufacturing paper and board
US8491755B2 (en) * 2002-10-24 2013-07-23 M-Real Oyj Method for manufacturing paper and board
US20080006380A1 (en) * 2006-05-19 2008-01-10 Abitibi-Consolidated, Inc. Coated Mechanical Pulp Paper
US20080041275A1 (en) * 2006-08-17 2008-02-21 Colin Wayne Hansen UV varnish gloss performance using novel pigment and process for making same
US7468101B2 (en) * 2006-08-17 2008-12-23 Specialty Minerals (Michigan) Inc. UV varnish gloss performance using novel pigment and process for making same
US9435079B2 (en) 2012-05-25 2016-09-06 Hewlett-Packard Development Company, L.P. Uncoated recording media
US9068292B2 (en) 2013-01-30 2015-06-30 Hewlett-Packard Development Company, L.P. Uncoated recording media

Also Published As

Publication number Publication date
AU2002366533B2 (en) 2008-03-06
FI116573B (sv) 2005-12-30
EP1458929A1 (en) 2004-09-22
AU2002366533A1 (en) 2003-06-23
WO2003050355A1 (en) 2003-06-19
NZ533042A (en) 2007-01-26
FI20012328A (sv) 2003-05-29
JP2005511916A (ja) 2005-04-28
CN1596327A (zh) 2005-03-16
CN1309904C (zh) 2007-04-11
CA2466899A1 (en) 2003-06-19
FI20012328A0 (sv) 2001-11-28

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