JP3641275B2 - 電気エネルギーの化学的源泉のための電極の製造方法 - Google Patents
電気エネルギーの化学的源泉のための電極の製造方法 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000126 substance Substances 0.000 title claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000002861 polymer material Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 229910001453 nickel ion Inorganic materials 0.000 claims description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 238000005341 cation exchange Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims 1
- 229910010277 boron hydride Inorganic materials 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
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- C—CHEMISTRY; METALLURGY
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
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- C23C18/1655—Process features
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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- H01M4/24—Electrodes for alkaline accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/64—Carriers or collectors
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Inorganic Chemistry (AREA)
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- Battery Electrode And Active Subsutance (AREA)
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Description
本発明は総合すると、電気エネルギーの化学的源泉のための電極、とくに蓄電器の電極を製造する方法に関するものである。さらに詳細には、本発明は基材として高分子材料を有する電極を製造する方法に関するものである。本発明はまた、ここに提案された方法を使用して製造された電極も包含するものである。
背景技術
現在の技術状態においては高分子を基材とした電気エネルギーの化学的源泉は知られている。フランス国特許出願第2,472,842号はその例示として引用される。この出願によれば、電極は金属被覆基材の上に活性物質が沈着されたものから製造される。
FRG特許第4,994,106号(1991年)に開示されているそのような公知の電極製造方法は、高分子材料、とくにポリオレフィン繊維から製造された不織布を、錫とパラジウムを含有する溶液中で活性化し、次いでこの基材を化学的および電気的メッキによりニッケルで被覆することからなる。
しかしながら、上記のような高分子基材の電極を製造する方法にはいろいろの欠点がある。すなわち、繊維質のポリマー材料を活性化するために、比較的高価なパラジウムを大量に使用することに起因する。
さらに、このように予備処理された材料の上に金属被覆を続けて形成することは、パラジウム粒子をポリマー表面から金属被覆の中に透過させやすく、結果的にこれを分解するおそれがある。
発明の開示
本発明の主たる目的は、高価な材料を使用する必要のない、ポリマーを基材とした電極を製造する新規な方法を提供するものである。
上記の目的は、本発明によって初めて提案されるカチオン交換性繊維材料を使用することによって達成される。これにより、あとで基材が被覆されるニッケルと同じ金属のイオンで飽和することにより、表面を活性化することが可能になった。
本発明による電極を製造する方法は次のとおりである。0.5〜6.0mg−eq/gのカチオン交換容量を有する繊維質ポリマー材料を使用する。この材料は事前に重炭酸ナトリウムの溶液で処理しておいてもよい。
ニッケルイオンの源泉としては硫酸ニッケルの溶液を使用してもよい。ここでは、ポリマー材料はそれがニッケルイオンで飽和されるに十分の時間まで維持される。それから、このニッケルイオンで処理された材料は、0.1〜1.2g/lの濃度のアルカリ金属の水素化ホウ素の水性溶中で、15〜70℃で、0.5〜30分で処理され。その結果、吸収されたニッケルは還元される。
そして、このように処理された材料は、通常の化学的および電気メッキ処理によりニッケルで被覆される。
発明の例示的形態
本発明のエッセンスを、以下の例示的態様により説明する。
実施例1
使用された繊維状ポリマーカチオン交換性材料は不織布を針侵入したフェルトであって、素材は放射線グラフトしたポリプロピレンで、イオン交換容量はニッケルに関して5mg−eq/g、繊維径は36mcm、気孔率87%、および厚さ5mmである。上記の材料は、重炭酸ナトリウムの2%水溶液に1時間浸漬され、脱イオン水で洗浄し、次いで、硫酸ニッケルの3%溶液で半時間処理することにより、ニッケルイオンで飽和した。このニッケル飽和された材料をもう一度洗浄し、ナトリウムボロンハイドライドの0.5g/l濃度の溶液で、30℃で15分間処理した。
上記のようにして処理した後では、材料は暗褐色に変わった。このようにして活性化された材料は、次の組成を有する溶液中で、室温で化学的にニッケル被覆された。
硫酸ニッケル 50g/l
塩化アンモニウム 35g/l
ナトリウムハイポホスファイト 40g/l
アンモニア pH=9まで
その後で、材料は、標準のワット(watts)電気メッキ槽中で、ニッケル含量が0.5g/cm3になるまでニッケルメッキされた。このようにして得られた電極基材の特性を以下の表に示す。
比較のために、表にはまたホッペケ社(Hoppecke)により電極として使用される材料の特性も併記する。
上記の表から分かるように、主要なそして最も重要な電極特性によれば、本発明により製造される基材は、ホ ッペケ社により得られる電極基材に非常に近いことが分かる。
Claims (7)
- 繊維状高分子材料が電極基材として使用され、その表面は活性化され、次いでニッケルで被覆される電気エネルギーの化学的源泉のための電極の製造方法において、該電極基材はカチオン交換性繊維状高分子材料であり、その表面をニッケルイオンで飽和させ、次い でアルカリ金属のボロンハイドライド溶液で処理することによって活性化することを特徴とする製造方法。
- カチオン交換容量0.5〜6.0mg−eq/gのカチオン交換性繊維状高分子材料を使用することを特徴とする、請求の範囲第1項に記載の製造方法。
- 高分子材料をニッケルイオンで飽和するために、該材料が硫酸ニッケル溶液中に保持されることを特徴とする、請求の範囲第2項に記載の製造方法。
- 高分子材料を硫酸ニッケル溶液に入れる前に、該高分子材料を重炭酸ナトリウムの水溶液中に保持し、脱イオン水で洗浄することを特徴とする、請求の範囲第1項ないし第3項のいずれか1項に記載の製造方法。
- ニッケルイオンで飽和された高分子材料が、0.1〜1.2g/lの濃度のナトリウムボロンハイドライドの水溶液で、15〜70℃で0.5〜30.0分間処理されることを特徴とする、請求の範囲第1項ないし第4項のいず れか1項に記載の製造方法。
- 請求の範囲第1項ないし第5項のいずれか1項に記載の製造方法により製造された、電気エネルギーの化学的源泉のための電極。
- 請求の範囲第1項ないし第5項のいずれか1項に記載の製造方法により製造された少なくとも1つの電極を有する、電気エネルギーの化学的源泉。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/RU1995/000170 WO1997007554A1 (en) | 1992-11-02 | 1995-08-14 | Method of manufacturing electrodes for chemical current sources |
Publications (2)
Publication Number | Publication Date |
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JPH10507873A JPH10507873A (ja) | 1998-07-28 |
JP3641275B2 true JP3641275B2 (ja) | 2005-04-20 |
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Application Number | Title | Priority Date | Filing Date |
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JP50919097A Expired - Fee Related JP3641275B2 (ja) | 1995-08-14 | 1995-08-14 | 電気エネルギーの化学的源泉のための電極の製造方法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US6063143A (ja) |
EP (1) | EP0784351A4 (ja) |
JP (1) | JP3641275B2 (ja) |
KR (1) | KR100332321B1 (ja) |
BG (1) | BG61922B1 (ja) |
CA (1) | CA2202384C (ja) |
CZ (1) | CZ286186B6 (ja) |
NO (1) | NO315447B1 (ja) |
WO (1) | WO1997007554A1 (ja) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6222723B1 (en) | 1998-12-07 | 2001-04-24 | Joint Stock Company “Elton” | Asymmetric electrochemical capacitor and method of making |
JP2001313038A (ja) * | 2000-02-21 | 2001-11-09 | Mitsubishi Materials Corp | アルカリ2次電池用集電材及びその製造方法並びにそれを用いたアルカリ2次電池 |
WO2006036077A1 (fr) * | 2004-08-31 | 2006-04-06 | Sergey Nikolaevich Razumov | Procede de fabrication d'une electrode non polarisable pour condensateur electrochimique |
EP1894215A1 (en) * | 2005-06-24 | 2008-03-05 | Universal Supercapacitors Llc. | Current collector for double electric layer electrochemical capacitors and method of manufacture thereof |
EP1897104A1 (en) * | 2005-06-24 | 2008-03-12 | Universal Supercapacitors Llc. | Heterogeneous electrochemical supercapacitor and method of manufacture |
CA2612642A1 (en) * | 2005-06-24 | 2007-01-04 | Valery Pavlovich Nedoshivin | Electrode and current collector for electrochemical capacitor having double electric layer and double electric layer electrochemical capacitor formed therewith |
US7919014B2 (en) | 2006-11-27 | 2011-04-05 | Universal Supercapacitors Llc | Electrode for use with double electric layer electrochemical capacitors having high specific parameters |
RU2744516C1 (ru) * | 2020-06-26 | 2021-03-11 | Акционерное общество "Энергия" | Способ изготовления неполяризуемого электрода электрохимического конденсатора |
Family Cites Families (20)
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US3351487A (en) * | 1963-11-06 | 1967-11-07 | Dow Chemical Co | Process for plating permeable membrane |
US4039714A (en) * | 1971-05-28 | 1977-08-02 | Dr. -Ing. Max Schloetter | Pretreatment of plastic materials for metal plating |
US3962494A (en) * | 1971-07-29 | 1976-06-08 | Photocircuits Division Of Kollmorgan Corporation | Sensitized substrates for chemical metallization |
US3900601A (en) * | 1973-09-28 | 1975-08-19 | Ppg Industries Inc | Treatment of thin metallic films for increased durability |
US4211829A (en) * | 1977-04-27 | 1980-07-08 | Compagnie Generale Des Etablissements Michelin | Process for assembling a porous membrane on a support and assembly produced in this manner |
FR2472842A1 (fr) * | 1979-07-06 | 1981-07-03 | Sorapec | Structure d'electrode pour generateur electrochimique |
DE3048157A1 (de) * | 1979-12-21 | 1981-08-27 | RAI Research Corp., 11787 Haupaugue, N.Y. | Membrane fuer elektrochemische zellen, verfahren zu ihrer herstellung und ihre verwendung in primaer- und sekundaerelementen |
US4331521A (en) * | 1981-01-19 | 1982-05-25 | Oronzio Denora Impianti Elettrochimici S.P.A. | Novel electrolytic cell and method |
FR2518126B1 (fr) * | 1981-12-14 | 1986-01-17 | Rhone Poulenc Spec Chim | Procede de metallisation d'articles electriquement isolants en matiere plastique et les articles intermediaires et finis obtenus selon ce procede |
FR2544341A1 (fr) * | 1983-04-15 | 1984-10-19 | Rhone Poulenc Rech | Procede de metallisation de films souples electriquement isolants et articles obtenus |
JPS61101959A (ja) * | 1984-10-25 | 1986-05-20 | Meidensha Electric Mfg Co Ltd | 亜鉛/臭素電池の電極 |
JPS61101960A (ja) * | 1984-10-25 | 1986-05-20 | Meidensha Electric Mfg Co Ltd | 亜鉛―臭素電池の負極電極 |
KR910001950B1 (ko) * | 1987-11-27 | 1991-03-30 | 페르메렉 덴꾜꾸 가부시끼가이샤 | 전극 구조물 및 그 제조 방법 |
DE69014183T2 (de) * | 1989-09-18 | 1995-06-22 | Toshiba Battery | Nickel-Metallhydridsekundärzelle. |
DE3940407A1 (de) * | 1989-12-04 | 1991-06-06 | Schering Ag | Verfahren zur galvanischen direktmetallisierung |
JPH04234765A (ja) * | 1990-08-29 | 1992-08-24 | Xerox Corp | 基体、ベルトおよび静電写真像形成部材、並びにこれらの製造方法 |
US5414140A (en) * | 1992-01-21 | 1995-05-09 | E. I. Du Pont De Nemours And Company | Process for making fluorinated aldehydes |
JP2673078B2 (ja) * | 1992-05-27 | 1997-11-05 | 東芝電池株式会社 | アルカリ二次電池用のペースト式電極 |
US5458955A (en) * | 1993-10-21 | 1995-10-17 | Monsanto Company | Metal/polymer laminates having an anionomeric polymer film layer |
JPH07320742A (ja) * | 1994-05-20 | 1995-12-08 | Sumitomo Electric Ind Ltd | アルカリ蓄電池用電極およびその製造方法 |
-
1995
- 1995-08-14 US US08/817,254 patent/US6063143A/en not_active Expired - Lifetime
- 1995-08-14 EP EP95929267A patent/EP0784351A4/en not_active Withdrawn
- 1995-08-14 CZ CZ19971074A patent/CZ286186B6/cs not_active IP Right Cessation
- 1995-08-14 CA CA002202384A patent/CA2202384C/en not_active Expired - Fee Related
- 1995-08-14 KR KR1019970701863A patent/KR100332321B1/ko not_active IP Right Cessation
- 1995-08-14 WO PCT/RU1995/000170 patent/WO1997007554A1/ru active IP Right Grant
- 1995-08-14 JP JP50919097A patent/JP3641275B2/ja not_active Expired - Fee Related
-
1997
- 1997-04-10 NO NO19971639A patent/NO315447B1/no not_active IP Right Cessation
- 1997-04-10 BG BG101405A patent/BG61922B1/bg unknown
Also Published As
Publication number | Publication date |
---|---|
CA2202384C (en) | 2005-11-01 |
CZ286186B6 (cs) | 2000-02-16 |
NO315447B1 (no) | 2003-09-01 |
BG101405A (en) | 1997-07-31 |
WO1997007554A1 (en) | 1997-02-27 |
NO971639L (no) | 1997-04-10 |
CZ107497A3 (en) | 1997-10-15 |
KR100332321B1 (ko) | 2002-06-20 |
CA2202384A1 (en) | 1997-02-27 |
KR970706619A (ko) | 1997-11-03 |
EP0784351A4 (en) | 2000-02-09 |
EP0784351A1 (en) | 1997-07-16 |
US6063143A (en) | 2000-05-16 |
NO971639D0 (no) | 1997-04-10 |
BG61922B1 (bg) | 1998-09-30 |
JPH10507873A (ja) | 1998-07-28 |
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