EP1475476A1 - Procédé permettant d'ameliorer la retention et la drainage dans la fabrication de papier, de carton mince et de carton - Google Patents

Procédé permettant d'ameliorer la retention et la drainage dans la fabrication de papier, de carton mince et de carton Download PDF

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Publication number
EP1475476A1
EP1475476A1 EP20040076330 EP04076330A EP1475476A1 EP 1475476 A1 EP1475476 A1 EP 1475476A1 EP 20040076330 EP20040076330 EP 20040076330 EP 04076330 A EP04076330 A EP 04076330A EP 1475476 A1 EP1475476 A1 EP 1475476A1
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EP
European Patent Office
Prior art keywords
retention
added
drainage
chemical
liquid
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.)
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Application number
EP20040076330
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German (de)
English (en)
Inventor
German Vergara Lopez
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Individual
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Individual
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Publication date
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Publication of EP1475476A1 publication Critical patent/EP1475476A1/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
    • D21H23/76—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
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • 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
    • D21H17/53—Polyethers; Polyesters
    • 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
    • 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
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • 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
    • 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

Definitions

  • the present invention generally refers to the manufacturing process of paper, paperboard, cardboard and similar products (such as cellulose, fiber cement, etc.) in which, at different points of the wet end of the machine, an enhanced, concentrated, liquid smectite (avoiding herewith the need of an on-site preparation unit) and a natural or synthetic polymer are added.
  • paper, paperboard, cardboard and similar products such as cellulose, fiber cement, etc.
  • the said retention and drainage agents can be added in any order, thus improving the retention, drainage, formation and drying, without affecting the whiteness and enhancing the physical values of the paper, paperboard, cardboard and other similar products.
  • the retention and drainage systems aim at improving the drainage (the capacity to eliminate water) and the retention of fines and fillers which are part of the paper sheet.
  • the amount of bentonite included in the pulp is generally between 0.02 and 2% by weight dry bentonite clay, based on dry weight of paper or pulp, and most preferably it is between 0.1 and 1%.
  • the bentonite-type clay used in the invention may be one of the common commercially available bentonites (known as montmorillonite clays) such as "Wyoming bentonite” and "Fullers Earth", and may or may not be chemically modified, e.g. by alkali treatment to convert the calcium bentonite substantially to alkali (e.g. sodium, potassium or ammonium)bentonite.
  • the microparticulate aid is preferably bentonite, silica, a polysilicic acid, polysilicate microgel, or an aluminum-modified version thereof.
  • silicate microparticles together with a cationic polymer in a retention system is described in the US Patent 5.194.120 of Delta Chemicals.
  • the prevalent cation in the synthetic amorphous metal silicate was magnesium, and the polymer was preferably a terciary or quaternary amine derivative of polyacrylamide, their weight ratio being between 0.03:1 and 30:1.
  • ORGANOPOL system described in Patent N° EP-A-0 235893, granted in the year 1979, consisted of two chemical products:
  • the polymer added at this point does not allow to reduce the size of the floccules, no smaller, tougher and more uniform floccules are obtained, and therefore there is no good formation of the paper, paperboard or cardboard sheet.
  • the ORGANOPOL system presents the following disadvantages: loss of whiteness, with the consequent increase of the use of optical whiteners, the adverse impact of the retention and drainage and the complex handling of the bentonite.
  • That patent is based on cationic linear polymers of high molecular weight before a shearing stage, and after the shearing stage the clay (bentonite) is added. Preferably at the last shearing point, which is the pressure screen.
  • System Component 1 Component 2
  • Component 3 Particol (CIBA) Cationic polyacrylamide Colloidal silica Poliflex (CIBA) Cationic polyacrylamide Inverse anionic micro-emulsion Composil (EKA) Cationic starch with high substitution degree Polysilicic acid Positek (Nalco) Cationic coagulant High molecular weight flocculant Borosilicate Mosaic (Buckman) Coagulant Polyacrylamide Microparticle (4 alternatives)
  • Particol has the advantage of using low application doses and its on-site preparation diminishes the possibility of losing effectiveness.
  • the counterpart is the complex equipment at the client's plant.
  • Composil is a system which has good retention and drainage results, does not effect the strength properties and does not have any impact on the consumption of optical whiteners.
  • the problem is that it is only effective in alkaline systems, it is expensive and good control must be kept on the dose (equipment).
  • Positek y Mosaic systems need more components, and therefore have more equipment and variables to control; they are more complex systems.
  • TOP DUAL a new retention and drainage system was developed, called “TOP DUAL", recommended for the manufacturing of paper, paperboard, cardboard and other similar products, for acid, neutral and alkaline environments, in which basically two products or chemical compositions are added to the paper stock:
  • Figure 1 shows the following treatment equipments relevant from retention and drainage treatment point of view, including the points where the products of the present invention can be added:
  • the novel secondary retention and drainage agent, VERSINQUI A-250 consists of a liquid formula, manufactured by the supplier, capable of being introduced via a pump and which contains as one of its main ingredients a smectite or a chemically modified version thereof, preferably a normal, activated or modified bentonite with a concentration in the formula higher than 6.5% by weight of the dispersion.
  • This secondary formula allows, among other things, to strongly increase the specific, superficial area of the before mentioned smectite with which the retention capacity of fines, colloidal particles, semi-colloidal particles, organic and inorganic compounds present in the paper stock with which paper, paperboard, cardboard and other similar products are manufactured, is improved.
  • the secondary agent VERSINQUI A-250 modifies the stock, which is flocculated by the action of the second component, called primary retention and drainage agent VERSINQUI.
  • the secondary retention and drainage agent, VERSINQUI A-250, of the present invention can be added to the paper machine in the following points of the process, indicated in Figure 1:
  • the secondary retention and drainage agent, object of the present invention the novel liquid product VERSINQUI A-250, more easily retains the organic and inorganic compounds present in the stock the paper, paperboard, cardboard and other similar products (cellulose, fiber cement, etc.) are manufactured with, such as fines, fillers, glues, starch, lignine and hemicelluloses.
  • VERSINQUI A-250 before the fan pump and the primary retention and drainage agent VERSINQUI, consisting of a linear, branched or cross-linked polyacrylamide apart from starches, polyethylene oxides, dry strength resins, wet strength resins, organic and inorganic coagulants and other polymers, before and inside the pressure screen (10a, 10b) of the paper machine allow to obtain a higher general first-pass retention in the said machines.
  • adding the secondary retention and drainage agent VERSINQUI A-250 and the primary retention and drainage agent VERSINQUI at the indicated points of the paper machine allows to obtain smaller, tougher and more uniform floccules, with which a better formation of the paper sheet is obtained and it allows to enhance the physical parameters of the paper, paperboard, cardboard and other similar products, such as the longitudinal strength, the transversal strength, CMT, ring crush, Cobb, Mullen explosion, Denisson, etc.
  • adding the secondary retention and drainage agent VERSINQUI A-250 and the primary retention and drainage agent VERSINQUI at the indicated points of the paper machine allows to work with lower consistences in the head box (11) of the paper machine, with which, among other things, a better distribution of the fibers in the wet sheet being formed on the wire or the vats is achieved.
  • adding the secondary retention and drainage agent VERSINQUI A-250 and the primary retention and drainage agent VERSINQUI according to the present invention allows to increase the drainage capacity of the paper stock, to produce a dryer sheet at the end of the wire or the vats, with which a substantial saving in the consumption of steam is achieved, apart from increasing the speed and with this the production of the paper machine and maintaining, moreover, the stability thereof.
  • the TOP DUAL retention and drainage system of the present invention it is possible to decrease the levels of dosage of the chemical product VERSINQUI A-250 to 150 g/ton of paper, equivalent to 40 g of smectite per ton/paper, and the polymer VERSINQUI to 50 g/ton paper, obtaining high levels of retention and drainage of the fiber very superior to those of the systems described in the prior art, for example the one called ORGANOPOL.
  • dosage levels a considerable saving in consumption and the consequent costs of the chemical products of the TOP DUAL retention and drainage system in the paper machine according to the invention is achieved.
  • the preferable dosage level of the secondary retention and drainage agent according to the invention lies between 150 and 1.000 g/ton of paper; however, the dosage of the formula of the prior art consisting of a powder bentonite (ORGANOPOL system) lies between 2.000 and 6.000 g/ton of paper, where, moreover, in this last case a very big and expensive unit is used in the continuous process of the preparation of the bentonite dispersion.
  • the said dosage of the retention and drainage agents VERSINQUI A-250/VERSINQUI according to the invention allows to improve the quality of the manufactured paper, complying with all the technical specifications and quality standards of the product manufactured in the paper machine.
  • ORGANOPOL product of the company CIBA consists of a linear cationic polyacrylamide described in the patent N° EP-A-0 235893, granted in the year 1979, is applied in the dual retention system ORGANOPOL and is added to the thin, diluted paper stock after the last point of major shearing of the machine, that is after the pressure screen (10c) and flocculates the modified stock.
  • the primary retention and drainage agent of the present invention consisting of a linear, branched or cross-linked polyacrylamide, apart from starches, polyethylene oxides, dry strength resins, wet strength resins, organic and inorganic coagulants and other polymers, can be added before and inside the pressure screen (10a, 10b) to allow, in the first place, for the formation of big floccules in the modified stock, which, while passing through the before mentioned pressure screen, form smaller, tougher and more uniform floccules, with which a better formation of the sheet of paper, paperboard, cardboard or other similar product without lumps in the stock is achieved.
  • the primary retention and drainage agent VERSINQUI after the pressure screen (10c).
  • Another advantage of the present invention through the process of adding VERSINQUI at the indicated adding points, is that it allows to reduce the tearing of the paper sheets and, consequently, to increase the productivity of the paper machine, reducing, moreover, the solids in suspension at the effluent of the machine or plant.
  • Another advantage of the invention lies in the fact that adding the retention agent VERSINQUI at the indicated points of the paper machine allows to reduce the dosages of starch, glue and other chemical agents, maintaining the values within the standard, reducing the BOD and COD indexes at the effluent of the paper machine with the consequent advantages from environmental contamination point of view.
  • system of the present invention allows to work in acid, neutral or alkaline environments and does not affect the whiteness of the paper.
  • VERSINQUI which is a linear, branched or cross-linked polyacrylamide or a starch, polyethylene oxide (PEO), dry strength resin, wet strength resin, organic or inorganic coagulant or another polymer, flocculates the stock.
  • Adding the primary retention and drainage agent VERSINQUI according to the invention can be done at the following points of the paper machine:
  • the primary retention and drainage agent VERSINQUI can be formed by the following components:
  • the before mentioned primary retention and drainage agent is preferably prepared in the client's plant. If the ingredients are solid products, then the dissolution thereof is effectuated in an automatic powder dissolution unit, and if they are liquids, then it is effectuated by means of an on-line dosage pump.
  • the dosage range of the primary retention agent lies between 50 and 10.000 g/ton of paper.
  • the first stage for adding the chemical products of the retention and drainage system called TOP DUAL according to the present invention is developed in the refined or non-refined stock tank (1 a).
  • This refined or non-refined stock is the result of the disintegration of the fibrous material: rags of cellulose, waste paper and brokers, etc., produced in the so-called “helix” or “pulper” according to a production schedule.
  • a liquid chemical composition with retention and drainage properties according to the invention is added.
  • This chemical composition corresponds to the product VERSINQUI A-250, secondary retention and drainage agent.
  • This stock with the agent VERSINQUI A-250 goes to the fan pump (9), pressure screen (10) and then to the head box (11). There are nine other possible points of adding, mentioned before, adequate for introducing the agent VERSINQUI A-250 to the paper stock to manufacture paper, paperboard, cardboard and similar products.
  • VERSINQUI A-250 which is a liquid, pumpable product, manufactured in the plant of the supplier and which contains a smectite or a chemically modified version thereof, preferably a normal, activated or modified bentonite, is very easy, since it is preferably distributed in containers of 1.000 kg and a variable caudal pump is sufficient to adequately add this product. It is a simple installation: on a container, a second container is installed on a stand with the 1.000 kg of VERSINQUI A-250 product which is unloaded according to what the lower container consumes. Finally, during the course of the days, what is left inside the upper container is emptied and the container is changed. The lower container is connected to the dosage pump.
  • This first liquid composition corresponding to the secondary retention and drainage agent called VERSINQUI A-250 has the following chemical formula: General formula: Water (from 5 to approx. 95° C) 0 - 92%, by weight; Dispersing agent 1 - 80%, by weight and Smectite (clay) 8 - 50% by weight.
  • this first liquid composition of the secondary agent VERSINQUI A-250 prepared in the supplier's plant, allows for a de-lamination of the smectite (clay) and, therefore, the specific, superficial area of the smectite is strongly increased, with which an increase in the retention of fines, colloidal particles, semi-colloidal particles of the organic and inorganic compounds present in the paper stock for the manufacturing of paper, paperboard, cardboard and other similar products, is achieved and this thus modified stock is flocculated by the second component, the so-called primary retention and drainage agent.
  • the pumpable liquid chemical composition of the secondary retention and drainage agent VERSINQUI A-250 allows to concentrate the smectite clay 6.5% by weight in the watery dispersion, situation not one single system in use in the world currently achieves.
  • the dosage controlled via a pump with variable caudal of the VERSINQUI A-250 lies preferable between 150 and 1.000 g/ton of final produced paper.
  • the dispersing agent of the before mentioned formula is preferably a sodium polyacrylate.
  • the second stage of the method according to the invention comprises adding the liquid composition or chemical product, called primary retention and drainage agent or VERSINQUI, which can be a:
  • the adding points of the before mentioned primary retention agent can be between the positions 1a to 10c of the stream drawing of Figure 1. Adding the primary retention and drainage agent VERSINQUI is preferably done at the following points:
  • the preparation and adding of the primary retention and drainage agent is preferably in the paper factory of the client. If the products are solid, then the dissolution is done in an automatic powder dissolution unit and if they are liquids, it is done by means of an on-line dilution dosing pump.
  • the dosage range of the primary retention and drainage agent lies between 50 and 10.000 g/ton final paper.
  • the sequence of adding the two chemical compositions or the chemical products can be done indistinctly; that is, first the secondary retention and drainage agent and then the primary, or vice versa, first the primary retention and drainage agent and then the secondary. Additionally, in some cases the secondary retention and drainage agent can be used without the primary retention and drainage agent.

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EP20040076330 2003-05-05 2004-05-03 Procédé permettant d'ameliorer la retention et la drainage dans la fabrication de papier, de carton mince et de carton Withdrawn EP1475476A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CL9042003 2003-05-05
CL2003000904 2003-05-05

Publications (1)

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EP1475476A1 true EP1475476A1 (fr) 2004-11-10

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Country Status (8)

Country Link
US (1) US20040221977A1 (fr)
EP (1) EP1475476A1 (fr)
JP (1) JP2004332193A (fr)
CN (1) CN100532717C (fr)
AR (1) AR044156A1 (fr)
BR (1) BRPI0401695A (fr)
CA (1) CA2466312C (fr)
MX (1) MXPA04003942A (fr)

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WO2006069660A1 (fr) * 2004-12-22 2006-07-06 Basf Aktiengesellschaft Procede de fabrication de papier, de carton-pate et de carton
CN102242522A (zh) * 2010-04-07 2011-11-16 浙江凯丰纸业有限公司 一种用于双向组合式造纸增强工艺的装置
CN101400854B (zh) * 2006-03-16 2012-06-27 住友精化株式会社 抄纸方法和抄纸机

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US9752283B2 (en) 2007-09-12 2017-09-05 Ecolab Usa Inc. Anionic preflocculation of fillers used in papermaking
CN103422395B (zh) * 2012-05-15 2016-03-02 纳尔科公司 在造纸中增强脱水、纸片湿纸幅强度和湿强度的方法
US8088250B2 (en) 2008-11-26 2012-01-03 Nalco Company Method of increasing filler content in papermaking
US8404083B2 (en) * 2008-08-18 2013-03-26 Basf Se Process for increasing the dry strength of paper, board and cardboard
CN101634120B (zh) * 2009-08-25 2011-12-28 陕西科技大学 一种提高纸料助留助滤性能的方法
FI124202B (en) * 2012-02-22 2014-04-30 Kemira Oyj A method for improving the process of making paper or paperboard using recycled fibrous material
US9200408B2 (en) * 2012-11-02 2015-12-01 Ecolab Usa Inc. Method of delivering a pigment dispersion and retention aid to a papermaking process
CN103850150A (zh) * 2014-03-27 2014-06-11 潍坊恒联美林生活用纸有限公司 一种工业无尘擦试纸制造工艺
CN107460770A (zh) * 2017-06-30 2017-12-12 安徽中亚纸业有限公司 一种纸浆环保纸浆脱水剂
AU2019209164B2 (en) 2018-01-16 2022-12-08 Solenis Technologies Cayman, L.P. Process for making paper with improved filler retention and opacity while maintaining wet tensile strength
CN109024041A (zh) * 2018-08-03 2018-12-18 广州市宏晓包装制品有限公司 一种纸浆脱水助剂
US10961662B1 (en) 2019-12-23 2021-03-30 Polymer Ventures, Inc. Ash retention additive and methods of using the same
CN111979843A (zh) * 2020-08-24 2020-11-24 山鹰国际控股股份公司 一种改善纸张表面平滑度的湿端造纸工艺

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CA2466312C (fr) 2012-07-10
HK1072085A1 (zh) 2005-08-12
CN1576460A (zh) 2005-02-09
CN100532717C (zh) 2009-08-26
CA2466312A1 (fr) 2004-11-05
US20040221977A1 (en) 2004-11-11
AR044156A1 (es) 2005-08-24
MXPA04003942A (es) 2007-06-29

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