WO2002060660A1 - Furan polymer impregnated wood - Google Patents
Furan polymer impregnated wood Download PDFInfo
- Publication number
- WO2002060660A1 WO2002060660A1 PCT/NO2002/000043 NO0200043W WO02060660A1 WO 2002060660 A1 WO2002060660 A1 WO 2002060660A1 NO 0200043 W NO0200043 W NO 0200043W WO 02060660 A1 WO02060660 A1 WO 02060660A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- wood
- curing
- furan polymer
- polymer impregnated
- impregnated wood
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
- B27K3/156—Combined with grafting onto wood fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/02—Condensation polymers of aldehydes or ketones only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/14—Furfuryl alcohol polymers
Definitions
- the invention described herein relates to a furan polymer impregnated wood which is uniform in colour and density throughout the treated zone.
- a parent wood has been impregnated with a polymerizable furfural alcohol monomer solution containing at least water, stabilizers, and furfuryl alcohol, and at least one further compound.
- the invention also relates to a method for preparing a furan polymer impregnated wood and uses thereof.
- An example of approach ii) is the subject of a previous invention disclosed by Schneider (NO-A-20005137) based on furfuryl alcohol (FA) treating formulations.
- This previous invention used an undiluted treating solution, and treated the wood to high levels of retention.
- specific gravity near 0.30 (such as pine)
- the retention of chemical may approach 200% of the weight of the dry wood.
- denser woods about 0.60 specific gravity, such as maple and beech retention can be in the 100% range.
- This level of retention has been shown to give excellent protection from biodeterioration, high dimensional stability in varying moisture conditions and an increase in most mechanical properties, particularly hardness.
- the main disadvantage with this treatment is the large amount of chemical used and the resulting cost.
- Furfuryl alcohol is highly water soluble and therefore easily forms a uniform solution with water which can be used to impregnate wood. Therefore, FA impregnating solutions containing different amounts of water are easily made.
- the solution must be polymerized to be useful.
- the polymerization must occur in wet or dry wood.
- the polymerization must occur at fairly low temperatures.
- Chemical initiators therefore must be added to the FA to make it polymerize in the desired temperature range and in wet or dry wood. How to initiate FA and make it polymerize in the desired temperature range is known from NO-A-20005137. However, the initiated FA from that technology does not mix well with water. Combing them causes the mixtures to separate into two components which cannot be uniformly impregnated into wood.
- One object of the invention is to provide a furan polymer impregnated wood by altering the wood cell wall with the same chemical monomer as that disclosed in NO-A-20005137 but using smaller amounts of chemical.
- a furan polymer impregnated wood characterized by wood impregnated with a polymerizable furfural alcohol monomer solution containing at least water, stabilizers, furfuryl alcohol, and one further compound selected from maleic anhydride, phthalic anhydride, maleic acid, malic acid, phthalic acid, and combinations thereof.
- a method for preparing a furan polymer impregnated wood characterized in that the wood is impregnated by one impregnation step with polymerizable furfural alcohol monomer solution containing at least water, stabilizers, and furfuryl alcohol, and at least one further compound selected from the group consisting of anhydrides, acids and combinations thereof, followed by a curing step.
- Two keys to the invention are 1) the use of one or more chemicals acting as new initiators and 2) the use of stabilizers which allows the initiated monomer to be water soluble.
- the initiators have similar affinity for wood as furfuryl alcohol and therefore enter the wood and remain in solution as deeply as it penetrates.
- the initiators are selected from any anhydride-containing compound as well as acids selected from the group of maleic acid, malic acid, phthalic acid, and stearic acid. However, preferably a compound selected from maleic anhydride, malic anhydride, phthalic anhydride and combinations thereof is used. More preferably, maleic anhydride or phthalic anhydride or a combination thereof is used, most preferably maleic anhydride or phthalic anhydride.
- the stabilizers are borax and lignosulfonic acids. To make a treating solution, at least one of the initiators, preferably one of these initiators only, and both of the stabilizers are dissolved in water. Furfuryl alcohol is then added, forming a solution which has several months useful life at room temperature.
- an oscillating pressure method may be used.
- Times of all of these processes depend upon many factors, including capability of equipment, size of wood, species of wood and penetration desired.
- Impregnation method generally used (full cell process) in accordance with the present invention will depend on treatment loading desired, such as follows: i) loading vessel with wood and securing the load so it will not float (if using air pressure, i.e., not a fluid pressure pump system), ii) closing door and drawing an appropriate partial vacuum, iii) filling the vessel with the treating solution, iv) pressurizing the submerged wood to a pressure in the range of 7 to 10 bar (100-150 psi) depending on wood species or other factors. Pressurizing for
- Wood moisture content must be below fiber saturation point (about 30% MC) in the zone to be treated. The further below, the more chemical which can be impregnated. If a specific target amount of chemical is required, the moisture content of the wood and the amount of solution impregnated must be taken into account and the concentration of the treating chemical adjusted accordingly.
- the treating solution is mixed and may contain, based on the weight of a given amount of water: borax (3%), maleic anhydride (2,3%), sodium salt of ligno- sulfonic acid (5,5%), and furfuryl alcohol (30,0%).
- the mixing operation is started by heating the water to approximately 60°C to facilitate the addition of borax, maleic anhydride and lignosulfonic acid components.
- borax sodium bicarbonate
- maleic anhydride sodium bicarbonate
- lignosulfonic acid components sodium bicarbonate
- the solution is cooled to 20-25°C and then the furfuryl alcohol is blended in with stirring, and is stored at a temperature of 15-20°C.
- the curing can take place at a range of temperatures, starting at from about 25°C to about 140°C.
- the lower temperatures (below about 40°C) require a long time to cure (days or weeks).
- From about 70°C to about 100°C the curing time is hours. Above 100°C makes times even shorter but conditions are difficult because rapid drying can occur and break the wood.
- steam or hot, humid air curing in the temperature range of about 70-100°C works well at a fixed temperature within the range. Also, temperature can be increased as curing and drying proceeds. Essentially, this is conventional temperature kiln drying operation. Curing and drying in hot oil also works well at temperatures from 70 to 120°C, either a fixed temperature within the range or by increasing temperature within the range as curing and drying proceeds.
- the furfuryl alcohol will cure readily in this temperature range with the furfuryl alcohol/initiator ratio used. Material 10 to 20 mm thick will cure in just two or three hours, but drying to final moisture content takes longer.
- the starting material is a woody material, usually lumber, which includes plank (thick lumber), but can also be wood composites such as oriented strand board and particle board. Woody materials of any dimensions can be utilized.
- the length of the woody materials is important since the treating solution travels very fast along the length but very slow across the cross-section. With permeable woods like beech and birch, the uniformity of treatment is determined by how well the treating solution remains uniform as it travels along the length. When impregnation is complete, the permeable woody material formed by this method has uniform properties throughout. Colour, resistance to moisture and deterioration and mechanical properties are consistent throughout. The properties and colour of individual pieces of lumber treated this way depend upon the loading of polymer achieved. Different species of wood, and even different boards of the same species, may impregnate differently. However, resistance to moisture and deterioration are little affected by loading.
- Woody material including cheap types and scrap material, can be used to produce noble wood products such as imitation teak, mahogany, and others, and also provide them with novel properties like water resistance and simpler and reduced maintenance requirements.
- Maleic anhydride (MA) was the best polymerization initiator. It is also a desirable component because it is thought to act as a bonding agent to wood.
- Stabilizers were needed to keep the mixture uniform. Otherwise, it separated into two components and one settled to the bottom.
- the pH must be near neutral for a uniform, stable mixture to be formed and maintained. 4.
- the pH must be on the acid side for curing to occur.
- Borax sodium tetraborate decahydrate
- the mixture must impregnate and then cure throughout the wood, giving a uniform product.
- the monomer mixture containing 23.1% FA, and 5.1% each of MA and borax was selected for a uniformity-of-treating trial. The results are given in Table 2.
- concentration study showed that the solution introduced into wood at concentrations between about 8% and 39% progressively increase wood dimensions at impregnation, polymer loading and antiswell efficiency.
- concentration chosen for further work 31%) and the highest concentration water solution tested (39%) are compared to values for undiluted, initiated FA in Table 3.
- the weight loss values for each fungus and both species allows the treated wood to be classed as «highly resistant» to decay according to Standard EN 113.
Abstract
Description
Claims
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60201584T DE60201584T2 (en) | 2001-02-01 | 2002-02-01 | FURANPOLYMER IMPRESSED WOOD |
NZ527842A NZ527842A (en) | 2001-02-01 | 2002-02-01 | Furan polymer impregnated wood having uniform colour and density |
MXPA03006848A MXPA03006848A (en) | 2001-02-01 | 2002-02-01 | Furan polymer impregnated wood. |
APAP/P/2003/002851A AP1558A (en) | 2001-02-01 | 2002-02-01 | Furan polymer impregnated wood. |
CA2435765A CA2435765C (en) | 2001-02-01 | 2002-02-01 | Furan polymer impregnated wood |
EEP200300352A EE05266B1 (en) | 2001-02-01 | 2002-02-01 | Furanpol wood impregnated with wood |
JP2002560835A JP4190885B2 (en) | 2001-02-01 | 2002-02-01 | Furan polymer impregnated wood |
DK02711566T DK1368167T3 (en) | 2002-02-01 | 2002-02-01 | Furan polymer-impregnated wood |
PL362439A PL202785B1 (en) | 2001-02-01 | 2002-02-01 | Furan polymer impregnated wood |
EP02711566A EP1368167B1 (en) | 2001-02-01 | 2002-02-01 | Furan polymer impregnated wood |
AT02711566T ATE279308T1 (en) | 2001-02-01 | 2002-02-01 | FURAN POLYMER IMPREGNATED WOOD |
AU2002230310A AU2002230310B2 (en) | 2001-02-01 | 2002-02-01 | Furan polymer impregnated wood |
BRPI0206876-1B1A BR0206876B1 (en) | 2001-02-01 | 2002-02-01 | furan polymer impregnated wood and method for preparing a furan polymer impregnated wood |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO20010558 | 2001-02-01 | ||
NO20010558A NO313273B1 (en) | 2001-02-01 | 2001-02-01 | Furan polymer-impregnated wood, method of manufacture and uses thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002060660A1 true WO2002060660A1 (en) | 2002-08-08 |
Family
ID=19912083
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NO2002/000043 WO2002060660A1 (en) | 2001-02-01 | 2002-02-01 | Furan polymer impregnated wood |
Country Status (20)
Country | Link |
---|---|
US (2) | US7008984B2 (en) |
EP (1) | EP1368167B1 (en) |
JP (1) | JP4190885B2 (en) |
CN (1) | CN1328024C (en) |
AP (1) | AP1558A (en) |
AT (1) | ATE279308T1 (en) |
AU (1) | AU2002230310B2 (en) |
BR (1) | BR0206876B1 (en) |
CA (1) | CA2435765C (en) |
DE (1) | DE60201584T2 (en) |
EE (1) | EE05266B1 (en) |
ES (1) | ES2230473T3 (en) |
MX (1) | MXPA03006848A (en) |
NO (1) | NO313273B1 (en) |
NZ (1) | NZ527842A (en) |
PL (1) | PL202785B1 (en) |
PT (1) | PT1368167E (en) |
RU (1) | RU2276010C2 (en) |
WO (1) | WO2002060660A1 (en) |
ZA (1) | ZA200306780B (en) |
Cited By (8)
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WO2004011214A2 (en) | 2002-07-26 | 2004-02-05 | Wood Polymer Technologies Asa | Furan polymer impregnated wood |
CN1310744C (en) * | 2002-07-26 | 2007-04-18 | 木聚合物技术有限公司 | Furan polymer impregnated wood |
WO2008140323A1 (en) * | 2007-05-11 | 2008-11-20 | Kebony Asa | Modified wood and method for producing modified wood |
US8197948B2 (en) | 2000-10-12 | 2012-06-12 | Kebony AB | Furan polymer impregnated wood, method for preparing the polymer and uses thereof |
US9156185B2 (en) | 2009-04-09 | 2015-10-13 | Kebony Asa | Apparatus and operating systems for manufacturing impregnated wood |
US9975605B2 (en) | 2009-04-23 | 2018-05-22 | Kebony Asa | Decking |
WO2023145902A1 (en) * | 2022-01-28 | 2023-08-03 | 富士岡山運搬機株式会社 | Method for producing modified wooden material, 5-hmf resinification solution, and modified wooden material |
WO2023180473A1 (en) | 2022-03-23 | 2023-09-28 | Kebony As | Polymerizable solution for obtaining a furan polymer impregnated material |
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AU2003903242A0 (en) * | 2003-06-25 | 2003-07-10 | The University Of Melbourne | Process for the treatment of wood |
NO321301B1 (en) * | 2003-08-15 | 2006-04-18 | Wood Polymer Technologies Asa | Formulation for treating wood, including a mixture of solutions containing styrene and furfuryl alcohol, and processes for the preparation and use thereof |
US8167045B2 (en) * | 2003-08-26 | 2012-05-01 | Halliburton Energy Services, Inc. | Methods and compositions for stabilizing formation fines and sand |
US7766099B2 (en) * | 2003-08-26 | 2010-08-03 | Halliburton Energy Services, Inc. | Methods of drilling and consolidating subterranean formation particulates |
US7781052B2 (en) * | 2004-05-31 | 2010-08-24 | Sumitomo Forestry Co., Ltd. | Method for making particle board |
NZ551766A (en) * | 2006-12-04 | 2009-05-31 | Zelam Ltd | Use of a wood modifying composition which comprises a hydrophilic prepolymer and a crosslinking agent |
EP1946900A1 (en) * | 2006-12-15 | 2008-07-23 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Treatment of wood |
JP5202840B2 (en) * | 2006-12-27 | 2013-06-05 | 株式会社ザイエンス | Method for preserving wood-based materials |
US20090004495A1 (en) * | 2007-06-29 | 2009-01-01 | Marc Henry Schneider | High weight percent gain (WPG) furfural-urea modification of wood |
US20090143537A1 (en) * | 2007-11-29 | 2009-06-04 | Marc Henry Schneider | Melt-polymerization surface reinforcement and hardening of wood, wood products and other porous materials using oligimer and polymer solutes in polymerizable monomer solvent |
TWI397933B (en) * | 2008-02-22 | 2013-06-01 | Ind Tech Res Inst | Capacitive modules |
GB201008464D0 (en) | 2010-05-20 | 2010-07-07 | Kebony Asa | Process for polymer impregnating wood |
DE102011104025A1 (en) | 2010-06-11 | 2011-12-15 | Technische Universität Dresden | Method for modification of wood or wood materials, involves subjecting wood of chemical and thermal treatment, where same strength properties in thermal untreated wood are achieved during reduced emission at volatile organic components |
KR101024070B1 (en) | 2010-09-13 | 2011-03-22 | 주식회사 에코웰 | Wood modification composition and modified wood prepared therefrom |
SE535622C2 (en) * | 2010-11-29 | 2012-10-16 | Organowood Ab | Environmentally friendly wood treatment process |
CN202381966U (en) | 2011-05-03 | 2012-08-15 | 科博尼Asa | Deck or floor |
CN109465942B (en) * | 2018-10-19 | 2022-06-07 | 湖南桃花江竹材科技股份有限公司 | Three-dimensional stereo surface high-strength bamboo composite material and manufacturing method thereof |
CN109333719B (en) * | 2018-10-25 | 2021-01-05 | 北京林业大学 | Furfuryl alcohol resin wood modifier and preparation method and application thereof |
CN109531747B (en) * | 2018-12-20 | 2020-07-14 | 中国林业科学研究院木材工业研究所 | Preparation method of nano-material toughened furfuryl alcohol wood |
JP7116404B2 (en) | 2019-04-27 | 2022-08-10 | 株式会社テオリアランバーテック | Method for producing furan polymer impregnated wood |
JP7116403B2 (en) | 2019-04-27 | 2022-08-10 | 株式会社テオリアランバーテック | Method for producing furan polymer impregnated wood |
EP3882328A1 (en) | 2020-03-18 | 2021-09-22 | Kebony AS | Modified wood, modification solution, method of modification and use thereof |
WO2022025089A1 (en) * | 2020-07-29 | 2022-02-03 | 富士岡山運搬機株式会社 | Method for producing modified wood-based material, furan derivative resinification solution, and modified wood-based material |
CN114505935A (en) * | 2020-11-16 | 2022-05-17 | 深圳碳十四科技创新有限公司 | Preparation method of multifunctional micro-nano structure modified wood |
CN115070890B (en) * | 2022-07-07 | 2023-07-21 | 南京林业大学 | Dehydration reinforcement treatment method for saturated wooden cultural relics |
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-
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- 2002-02-01 PL PL362439A patent/PL202785B1/en unknown
- 2002-02-01 EP EP02711566A patent/EP1368167B1/en not_active Expired - Lifetime
- 2002-02-01 AP APAP/P/2003/002851A patent/AP1558A/en active
- 2002-02-01 CA CA2435765A patent/CA2435765C/en not_active Expired - Lifetime
- 2002-02-01 DE DE60201584T patent/DE60201584T2/en not_active Expired - Lifetime
- 2002-02-01 EE EEP200300352A patent/EE05266B1/en unknown
- 2002-02-01 US US10/060,302 patent/US7008984B2/en not_active Expired - Lifetime
- 2002-02-01 ES ES02711566T patent/ES2230473T3/en not_active Expired - Lifetime
- 2002-02-01 MX MXPA03006848A patent/MXPA03006848A/en active IP Right Grant
- 2002-02-01 AT AT02711566T patent/ATE279308T1/en active
- 2002-02-01 JP JP2002560835A patent/JP4190885B2/en not_active Expired - Lifetime
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- 2002-02-01 RU RU2003126439/04A patent/RU2276010C2/en active
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2003
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2005
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
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US8197948B2 (en) | 2000-10-12 | 2012-06-12 | Kebony AB | Furan polymer impregnated wood, method for preparing the polymer and uses thereof |
EP2042282A1 (en) | 2002-07-26 | 2009-04-01 | Kebony ASA | Furan polymer impregnated wood |
CN1310744C (en) * | 2002-07-26 | 2007-04-18 | 木聚合物技术有限公司 | Furan polymer impregnated wood |
US7381473B2 (en) | 2002-07-26 | 2008-06-03 | Kebony Asa | Furan polymer impregnated wood |
EP1526954B1 (en) * | 2002-07-26 | 2009-03-04 | Kebony ASA | Furan polymer impregnated wood |
WO2004011214A2 (en) | 2002-07-26 | 2004-02-05 | Wood Polymer Technologies Asa | Furan polymer impregnated wood |
US7858203B2 (en) | 2002-07-26 | 2010-12-28 | Kebony Asa | Furan polymer impregnated wood |
WO2004011214A3 (en) * | 2002-07-26 | 2004-09-10 | Wood Polymer Technologies Asa | Furan polymer impregnated wood |
WO2008140323A1 (en) * | 2007-05-11 | 2008-11-20 | Kebony Asa | Modified wood and method for producing modified wood |
US9156185B2 (en) | 2009-04-09 | 2015-10-13 | Kebony Asa | Apparatus and operating systems for manufacturing impregnated wood |
US9975605B2 (en) | 2009-04-23 | 2018-05-22 | Kebony Asa | Decking |
WO2023145902A1 (en) * | 2022-01-28 | 2023-08-03 | 富士岡山運搬機株式会社 | Method for producing modified wooden material, 5-hmf resinification solution, and modified wooden material |
WO2023180473A1 (en) | 2022-03-23 | 2023-09-28 | Kebony As | Polymerizable solution for obtaining a furan polymer impregnated material |
Also Published As
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US20060094801A1 (en) | 2006-05-04 |
ATE279308T1 (en) | 2004-10-15 |
CA2435765C (en) | 2013-08-06 |
ES2230473T3 (en) | 2005-05-01 |
DE60201584T2 (en) | 2005-11-10 |
RU2003126439A (en) | 2005-03-10 |
ZA200306780B (en) | 2004-08-30 |
NO313273B1 (en) | 2002-09-09 |
BR0206876B1 (en) | 2013-09-10 |
EE05266B1 (en) | 2010-02-15 |
AU2002230310B2 (en) | 2005-04-21 |
CN1328024C (en) | 2007-07-25 |
US20020192400A1 (en) | 2002-12-19 |
CA2435765A1 (en) | 2002-08-08 |
NO20010558D0 (en) | 2001-02-01 |
JP4190885B2 (en) | 2008-12-03 |
US7008984B2 (en) | 2006-03-07 |
PL202785B1 (en) | 2009-07-31 |
AP1558A (en) | 2006-01-24 |
MXPA03006848A (en) | 2004-05-14 |
EP1368167A1 (en) | 2003-12-10 |
DE60201584D1 (en) | 2004-11-18 |
JP2004520199A (en) | 2004-07-08 |
EP1368167B1 (en) | 2004-10-13 |
EE200300352A (en) | 2003-10-15 |
NO20010558L (en) | 2002-08-02 |
BR0206876A (en) | 2004-01-20 |
AP2003002851A0 (en) | 2003-09-30 |
CN1489512A (en) | 2004-04-14 |
NZ527842A (en) | 2004-08-27 |
PL362439A1 (en) | 2004-11-02 |
RU2276010C2 (en) | 2006-05-10 |
PT1368167E (en) | 2005-02-28 |
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