CA2460083A1 - Coating composition for metal substrates - Google Patents
Coating composition for metal substrates Download PDFInfo
- Publication number
- CA2460083A1 CA2460083A1 CA002460083A CA2460083A CA2460083A1 CA 2460083 A1 CA2460083 A1 CA 2460083A1 CA 002460083 A CA002460083 A CA 002460083A CA 2460083 A CA2460083 A CA 2460083A CA 2460083 A1 CA2460083 A1 CA 2460083A1
- Authority
- CA
- Canada
- Prior art keywords
- composition according
- coating
- coating composition
- binder
- primer
- 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.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract 8
- 229910052751 metal Inorganic materials 0.000 title claims abstract 6
- 239000002184 metal Substances 0.000 title claims abstract 6
- 239000008199 coating composition Substances 0.000 title claims 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract 15
- 239000011230 binding agent Substances 0.000 claims abstract 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract 8
- 239000000203 mixture Substances 0.000 claims abstract 6
- 239000000049 pigment Substances 0.000 claims abstract 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract 6
- 239000011248 coating agent Substances 0.000 claims abstract 5
- 238000000576 coating method Methods 0.000 claims abstract 5
- 229910052681 coesite Inorganic materials 0.000 claims abstract 4
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 4
- 229910052682 stishovite Inorganic materials 0.000 claims abstract 4
- 229910052905 tridymite Inorganic materials 0.000 claims abstract 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract 3
- -1 ammonium ions Chemical class 0.000 claims abstract 3
- 239000002987 primer (paints) Substances 0.000 claims 12
- 239000002245 particle Substances 0.000 claims 7
- 239000007787 solid Substances 0.000 claims 5
- 229910000831 Steel Inorganic materials 0.000 claims 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 4
- 239000010959 steel Substances 0.000 claims 4
- 238000000034 method Methods 0.000 claims 3
- 239000011347 resin Substances 0.000 claims 3
- 229920005989 resin Polymers 0.000 claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 2
- 229910001297 Zn alloy Inorganic materials 0.000 claims 2
- 239000008119 colloidal silica Substances 0.000 claims 2
- 239000004606 Fillers/Extenders Substances 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 239000006087 Silane Coupling Agent Substances 0.000 claims 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 238000005728 strengthening Methods 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000001039 zinc pigment Substances 0.000 claims 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to a composition for coating a metal substrate which is intended to be fabricated and overcoated, wherein the binder comprises an acqueous silica sol having a SiO2/M2O mole ratio, with M representing the total of alkali metal and ammonium ions, of at least 6:1, a nd wherein the ratio of the pigment volume concentration to the critical pigmen t volume concentration is smaller than 1.
Claims (16)
1. A composition for coating a metal substrate which is intended to be fabricated and overcoated, said composition comprising a silica binder, characterized in that the ratio of the pigment volume concentration to the critical pigment volume concentration of said composition is smaller than 1, and in that the binder comprises an aqueous silica sol and, optionally, a minor amount of alkali metal silicate, with the silica and/or silicate particles having an average size larger than 10 nm, and in that said binder has a SiO2/M2O mole ratio of at least 6:1, wherein M represents the total of alkali metal and ammonium ions.
2. A coating composition according to claim 1, characterized in that the pigment volume concentration is between 40 and 55%.
3. A coating composition according to claim 1 or 2, characterized in that the binder is a silica sol of SiO2/M2O mole ratio at least 25:1.
4. A coating composition according to any one of claims 1 to 3, characterized in that the binder comprises colloidal silica particles with an average particle size between 10 and 22 nm.
5. A coating composition according to claim 4, characterized in that the binder comprises colloidal silica particles with an average particle size between 10 and 16 nm.
6. A coating composition according to claim 5, characterized in that the aqueous silica sol has a pH in the range 9.5 to 11.
7. A coating composition according to any one of claims 1 to 6, characterized in that the primer coating further comprises 0 to 30% by weight of an organic resin, based on solid binder.
8. A coating composition according to claim 7, characterized in that the primer coating further comprises 10-20% by weight of an organic resin, based on solid binder.
9. A coating composition according to any one of claims 1 to 8, characterized in that the binder comprises an alumina surface-modified aqueous silica sol.
10. A coating composition according to claim 9, characterized in that the binder comprises 0.05 to 2.5 wt.% of alumina, calculated as the percentage by weight of Al2O3, based on the silica sol particles in the composition.
11. A coating composition according to any one of claims 1 to 10, characterized in that it is a water based shop primer.
12. A coating composition according to any one of claims 1 to 11, characterized in that the coating further comprises zinc powder and/or a zinc alloy.
13. Water based shop primer for the coating of steel substrates which are intended to be fabricated and overcoated, said composition having a solid content of 20 - 40% by volume, wherein the ratio of the pigment volume concentration to the critical pigment volume concentration is smaller than 1, comprising:
- an aqueous silica sol binder having a SiO2/M2O mole ratio of at least 6:1 and a pH between 9.5 and 11, wherein M represents the total of alkali metal and ammonium ions and wherein the optionally alumina modified silica particles have an average size between 10 nm and 16 nm, - 10 - 55% by volume of the coating on a dry film basis of zinc powder and/or a zinc alloy having a mean particle size in the range 2 to 12 µm, - 0 - 35% by weight, based on solid binder, of an organic resin, - 0 - 30% by weight, based on solid binder, of a silane coupling agent, - optionally non-zinc pigment(s), and - optionally a pot life extender.
- an aqueous silica sol binder having a SiO2/M2O mole ratio of at least 6:1 and a pH between 9.5 and 11, wherein M represents the total of alkali metal and ammonium ions and wherein the optionally alumina modified silica particles have an average size between 10 nm and 16 nm, - 10 - 55% by volume of the coating on a dry film basis of zinc powder and/or a zinc alloy having a mean particle size in the range 2 to 12 µm, - 0 - 35% by weight, based on solid binder, of an organic resin, - 0 - 30% by weight, based on solid binder, of a silane coupling agent, - optionally non-zinc pigment(s), and - optionally a pot life extender.
14. A process for primer coating a steel substrate wherein the metal is primer coated with a coating composition according to any one of claims 1-12 which is prepared using a silica sol of which the pH is adjusted to pH 9.5-11.
15. A process for primer coating a steel substrate wherein the metal is primer coated with a coating composition according to any one of claims 1-12 and wherein after the primer coating has dried to the extent that it is touch dry, it is optionally treated with a film strengthening solution.
16. A process for primer coating a steel substrate wherein the metal is primer coated with a coating composition according to any one of claims 1-12 and wherein after the primer coating has dried to the extent that it is touch dry, the coated substrate is immersed in water or alternatively kept in an atmosphere with a relative humidity of of least 50%.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2001/010552 WO2002022745A1 (en) | 2000-09-13 | 2001-09-11 | Primer coating of steel |
| EPEPO1/10552 | 2001-09-11 | ||
| PCT/EP2001/010635 WO2002022746A1 (en) | 2000-09-13 | 2001-09-13 | Primer coating of steel |
| EPEP/0110635 | 2001-09-13 | ||
| EP02250068.0 | 2002-01-07 | ||
| EP02250068 | 2002-01-07 | ||
| PCT/EP2002/009119 WO2003022940A1 (en) | 2001-09-11 | 2002-08-13 | Coating composition for metal substrates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2460083A1 true CA2460083A1 (en) | 2003-03-20 |
| CA2460083C CA2460083C (en) | 2012-04-03 |
Family
ID=26069223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2460083A Expired - Lifetime CA2460083C (en) | 2001-09-11 | 2002-08-13 | Coating composition for metal substrates |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US20050031790A1 (en) |
| EP (1) | EP1425353B1 (en) |
| JP (1) | JP4250080B2 (en) |
| CN (1) | CN1245462C (en) |
| AT (1) | ATE307175T1 (en) |
| BR (1) | BR0212424B1 (en) |
| CA (1) | CA2460083C (en) |
| DE (1) | DE60206784T2 (en) |
| DK (1) | DK1425353T3 (en) |
| ES (1) | ES2251615T3 (en) |
| MX (1) | MXPA04002292A (en) |
| RU (1) | RU2293750C2 (en) |
| WO (1) | WO2003022940A1 (en) |
Families Citing this family (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4648677B2 (en) * | 2004-10-22 | 2011-03-09 | 新日本製鐵株式会社 | Surface-treated metal plate, method for producing the same, and coating solution |
| PL1853675T3 (en) | 2005-01-25 | 2012-01-31 | Sigma Coatings Bv | A binder composition |
| JP5546097B2 (en) | 2006-06-23 | 2014-07-09 | 新日鐵住金株式会社 | Surface treatment metal material and metal surface treatment agent |
| EP2109645B1 (en) * | 2006-07-04 | 2014-09-24 | SigmaKalon B.V. | A paint composition |
| TWI477565B (en) | 2007-04-19 | 2015-03-21 | Akzo Nobel Coatings Int Bv | Coating composition for metal substrates |
| SI2190939T1 (en) * | 2007-09-14 | 2011-09-30 | Basf Se | Coating composition for foam particles, and method for the production of molded foam bodies |
| CN101925660A (en) * | 2007-11-26 | 2010-12-22 | 都柏林技术学院知识产权公司 | Organosilane coating composition and its application |
| US20090149591A1 (en) * | 2007-12-07 | 2009-06-11 | Yong Yang | Paint Compositions With Low- or Zero-VOC Coalescence Aids and Nano-Particle Pigments |
| CH704939B1 (en) * | 2008-03-10 | 2012-11-15 | Akzo Nobel Chemicals Int Bv | Translucent heat protection element with aluminate or boratmodifiziertem silica. |
| JP5467431B2 (en) * | 2008-04-04 | 2014-04-09 | 敏倫 森実 | Water-based inorganic zinc-rich coating composition |
| US20090281207A1 (en) * | 2008-05-06 | 2009-11-12 | John Stratton | De-polluting and self-cleaning epoxy siloxane coating |
| US7846866B2 (en) * | 2008-09-09 | 2010-12-07 | Guardian Industries Corp. | Porous titanium dioxide coatings and methods of forming porous titanium dioxide coatings having improved photocatalytic activity |
| EP2216371A1 (en) * | 2009-02-07 | 2010-08-11 | Cognis IP Management GmbH | Solvent-free water-soluble silane modified silicates |
| GB2473002A (en) * | 2009-08-25 | 2011-03-02 | Nippon Sheet Glass Co Ltd | Reinforcement structure for rubber articles and methods of preparation |
| JP5340090B2 (en) * | 2009-09-10 | 2013-11-13 | アイシン化工株式会社 | Aqueous coating agent and coating film |
| US8299151B1 (en) * | 2010-01-29 | 2012-10-30 | Advanced Concrete Technologies Llc | Protective coatings for inorganic substrates and associated methods |
| US8344057B1 (en) * | 2010-01-29 | 2013-01-01 | Advanced Concrete Technologies Llc | Protective coatings for organic substrates and associated methods |
| CN102211430B (en) * | 2010-04-09 | 2014-06-04 | 威士伯采购公司 | Waterborne autoweldable shop primer |
| KR101714826B1 (en) | 2010-09-14 | 2017-03-09 | 주고꾸 도료 가부시키가이샤 | Aqueous coating composition and corrosion prevention method using said aqueous coating composition |
| CN102086314B (en) * | 2010-11-04 | 2012-06-27 | 江苏麟龙新材料股份有限公司 | Water-soluble aluminum-zinc-silicon paint for marine climate-resistant anticorrosion treatment |
| EP3517585B1 (en) | 2011-03-08 | 2021-06-30 | Swimc, LLC | Method for coating a cargo container |
| DE102011084183A1 (en) | 2011-03-25 | 2012-09-27 | Evonik Degussa Gmbh | Aqueous silane-based anti-corrosive formulation |
| CN102872877B (en) * | 2011-07-15 | 2014-12-17 | 神华集团有限责任公司 | High-abrasion resistance lithium-containing iron series Fischer-Tropsch synthetic catalyst, catalyst bonding agent containing blending silica sol and preparation method and application thereof |
| CN102408220B (en) * | 2011-08-08 | 2013-05-15 | 华南理工大学 | A kind of all-in-one waterborne inorganic-organic hybrid architectural coating and preparation method thereof |
| DE102011082835A1 (en) * | 2011-09-16 | 2013-03-21 | Siemens Aktiengesellschaft | Coating material for corrosion protection and solar receiver with such a layer material |
| CN103360825B (en) * | 2012-03-31 | 2016-01-06 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of metal protection coating and uses thereof and hot-dip metal plated material |
| CN103360837B (en) * | 2012-03-31 | 2015-12-09 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of metal protection coating and uses thereof and hot-dip metal plated material |
| BR112014026411B1 (en) * | 2012-05-09 | 2021-07-27 | Akzo Nobel Chemicals International B.V. | AQUEOUS PAINT DISPERSION |
| RU2538878C2 (en) * | 2012-11-26 | 2015-01-10 | Общество с ограниченной ответственностью "Инновации. Технологии. Производство" | Composition for application of anticorrosion coating |
| KR101377627B1 (en) | 2012-12-31 | 2014-03-25 | 윤경민 | Coating composition with ceramic for eliminating surface exfoliation formation of metallic material by high temperature oxidation |
| US10577507B2 (en) * | 2013-03-16 | 2020-03-03 | Prc-Desoto International, Inc. | Alkaline cleaning compositions for metal substrates |
| RU2710814C2 (en) * | 2013-03-16 | 2020-01-14 | Прк-Десото Интернэшнл, Инк. | Sol-gel corrosion inhibiting compositions |
| JP2015034097A (en) * | 2013-08-07 | 2015-02-19 | 信越化学工業株式会社 | Aqueous silane coupling agent composition and manufacturing method thereof, surface treatment agent and article |
| CN105473233B (en) | 2013-08-23 | 2018-11-16 | 威士伯采购公司 | Water type shop primer |
| KR101552889B1 (en) | 2014-02-20 | 2015-09-15 | 윤경민 | Coating composition for preventing metalizing of molten material |
| TWI600795B (en) | 2014-04-11 | 2017-10-01 | 新日鐵住金股份有限公司 | Anticorrosion steel material and method for producing the same, anticorrosion method for steel and ballast tank |
| CN108473790A (en) * | 2015-05-22 | 2018-08-31 | 晓温-威廉姆斯公司 | Water base zinc-rich pre-structured priming paint |
| EP3199597A1 (en) * | 2016-01-29 | 2017-08-02 | Jotun A/S | Shop primer |
| JP6767150B2 (en) * | 2016-04-08 | 2020-10-14 | 中国塗料株式会社 | Manufacturing method of steel sheet with rust preventive coating |
| EP3452560A4 (en) | 2016-05-04 | 2020-04-08 | General Cable Technologies Corporation | Compositions and coatings formed thereof with reduced ice adherence and accumulation |
| JP6063088B1 (en) * | 2016-09-16 | 2017-01-18 | 日新製鋼株式会社 | Painted metal plate |
| JP6757220B2 (en) * | 2016-09-27 | 2020-09-16 | 日本パーカライジング株式会社 | Surface treatment agent for metal materials and its manufacturing method, and metal materials with surface treatment coating and its manufacturing method |
| CA3041298C (en) * | 2016-10-20 | 2023-08-29 | Sathish Kumar Ranganathan | Durable coating compositions and coatings formed thereof |
| EP3398998A1 (en) | 2017-05-03 | 2018-11-07 | Evonik Degussa GmbH | Aqueous brine-gel compound as storage-stable precursor for zinc-rich primers |
| CN110655811A (en) * | 2019-10-24 | 2020-01-07 | 广东工业大学 | A new type of environment-friendly chrome-free zinc-aluminum coating and preparation method thereof |
| CN112358802A (en) * | 2020-12-11 | 2021-02-12 | 成都新柯力化工科技有限公司 | Electroplating coating imitated nano water-based paint and preparation method thereof |
| CN113563748A (en) * | 2021-08-27 | 2021-10-29 | 江苏进华重防腐涂料有限公司 | Water-based inorganic zinc silicate shop primer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL296183A (en) * | 1963-01-30 | |||
| US3522066A (en) * | 1966-12-06 | 1970-07-28 | Lithium Corp | Process for preparing aqueous mixed lithium and sodium (and/or potassium) silicate solutions |
| US3620784A (en) * | 1968-01-24 | 1971-11-16 | Nasa | Potassium silicate-zinc coatings |
| US3721574A (en) * | 1968-08-06 | 1973-03-20 | R Schneider | Silicate coatings compositions |
| DE2734080A1 (en) * | 1977-07-28 | 1979-02-15 | Linde Ag | METHOD FOR SEPARATING METHANE FROM A RAW GAS CONTAINING METHANE |
| US4162169A (en) * | 1977-12-21 | 1979-07-24 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Alkali-metal silicate binders and methods of manufacture |
| US4479824A (en) * | 1983-05-04 | 1984-10-30 | Schutt John B | Silicate binders and coatings |
| DE3887509T2 (en) * | 1987-02-13 | 1994-06-01 | Fina Research S.A., Feluy | PRODUCTION OF AN IMPROVED PRIMER COMPOSITION. |
| US5246488A (en) * | 1988-03-31 | 1993-09-21 | Nippon Paint Co., Ltd. | Temporary rust resisting coating composition |
| US4902442A (en) * | 1988-10-24 | 1990-02-20 | The Dow Chemical Company | Stabilized mixtures of colloidal silica and soluble silicate and a method of producing porous silica compositions therefrom |
| JPH0813348B2 (en) * | 1988-11-08 | 1996-02-14 | シチズン時計株式会社 | Metal surface layer of accessories such as watch cases and method of forming the same |
| US6211262B1 (en) * | 1998-04-20 | 2001-04-03 | Spectra Group Limited, Inc. | Corrosion resistant, radiation curable coating |
| ATE268362T1 (en) * | 1999-03-18 | 2004-06-15 | Akzo Nobel Coatings Int Bv | COATING AGENT FOR METAL SUBSTRATES |
-
2002
- 2002-08-13 US US10/487,339 patent/US20050031790A1/en not_active Abandoned
- 2002-08-13 CN CN02817771.1A patent/CN1245462C/en not_active Expired - Lifetime
- 2002-08-13 RU RU2004110933/04A patent/RU2293750C2/en not_active IP Right Cessation
- 2002-08-13 DK DK02767383T patent/DK1425353T3/en active
- 2002-08-13 AT AT02767383T patent/ATE307175T1/en not_active IP Right Cessation
- 2002-08-13 ES ES02767383T patent/ES2251615T3/en not_active Expired - Lifetime
- 2002-08-13 WO PCT/EP2002/009119 patent/WO2003022940A1/en active Search and Examination
- 2002-08-13 JP JP2003527007A patent/JP4250080B2/en not_active Expired - Lifetime
- 2002-08-13 EP EP02767383A patent/EP1425353B1/en not_active Revoked
- 2002-08-13 CA CA2460083A patent/CA2460083C/en not_active Expired - Lifetime
- 2002-08-13 DE DE60206784T patent/DE60206784T2/en not_active Expired - Lifetime
- 2002-08-13 BR BRPI0212424-6A patent/BR0212424B1/en not_active IP Right Cessation
- 2002-08-13 MX MXPA04002292A patent/MXPA04002292A/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| JP4250080B2 (en) | 2009-04-08 |
| RU2004110933A (en) | 2005-10-10 |
| DK1425353T3 (en) | 2006-02-13 |
| MXPA04002292A (en) | 2004-06-29 |
| WO2003022940A1 (en) | 2003-03-20 |
| EP1425353A1 (en) | 2004-06-09 |
| US20050031790A1 (en) | 2005-02-10 |
| RU2293750C2 (en) | 2007-02-20 |
| BR0212424A (en) | 2004-08-03 |
| CN1553941A (en) | 2004-12-08 |
| BR0212424B1 (en) | 2012-07-24 |
| ATE307175T1 (en) | 2005-11-15 |
| EP1425353B1 (en) | 2005-10-19 |
| DE60206784T2 (en) | 2006-07-06 |
| ES2251615T3 (en) | 2006-05-01 |
| JP2005510584A (en) | 2005-04-21 |
| WO2003022940A8 (en) | 2003-12-31 |
| CN1245462C (en) | 2006-03-15 |
| CA2460083C (en) | 2012-04-03 |
| DE60206784D1 (en) | 2006-03-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request |