JP4882762B2 - Water molecule inclusion coordination polymer metal complex compound - Google Patents
Water molecule inclusion coordination polymer metal complex compound Download PDFInfo
- Publication number
- JP4882762B2 JP4882762B2 JP2007016749A JP2007016749A JP4882762B2 JP 4882762 B2 JP4882762 B2 JP 4882762B2 JP 2007016749 A JP2007016749 A JP 2007016749A JP 2007016749 A JP2007016749 A JP 2007016749A JP 4882762 B2 JP4882762 B2 JP 4882762B2
- Authority
- JP
- Japan
- Prior art keywords
- metal complex
- complex compound
- water molecule
- coordination polymer
- polymer metal
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Fuel Cell (AREA)
Description
本発明は、プロトン伝導性の高い水分子内包配位高分子金属錯体化合物に関する。本発明の水分子内包配位高分子金属錯体化合物は、固体高分子燃料電池のプロトン交換膜等に好適である。 The present invention relates to a water molecule inclusion coordination metal-metal complex compound having high proton conductivity. The water molecule inclusion coordination polymer metal complex compound of the present invention is suitable for a proton exchange membrane of a solid polymer fuel cell.
固体高分子燃料電池のプロトン交換膜として、特許文献１に、配位高分子金属錯体Ｒ２ｄｔｏａＭ（Ｒ：アルキル基、ｄｔｏａ：ジチオオキサミド）の層間に水分子を吸蔵させて室温でプロトン伝導性を有する化合物が開示されている。しかし、更に高いプロトン伝導性を得ることが求められている。特許文献２には更に上記錯体に水素を吸蔵させて室温で電子伝導性を具備させることが示されているが、プロトン伝導性は特に向上しない。 As a proton exchange membrane of a solid polymer fuel cell, Patent Document 1 describes that proton molecules are absorbed at room temperature by interposing water molecules between layers of coordination polymer metal complex R 2 dtoaM (R: alkyl group, dtoa: dithiooxamide). Compounds having are disclosed. However, it is required to obtain higher proton conductivity. Patent Document 2 discloses that the above complex is further allowed to absorb hydrogen and have electron conductivity at room temperature, but proton conductivity is not particularly improved.
これに対して、細孔内の水分子の個数を制御したものとして、非特許文献１には、１ユニットが〔Ｃｕ２（Ｃ６Ｈ２Ｎ２Ｏ４）２（Ｃ４Ｈ４Ｎ２）〕・２Ｈ２Ｏで表わされる組成を有し、該Ｃｕ元素とピラジン−２，３−ジカルボキシレートとから成る２次元構造同士がピラジンから成る支柱で相互に間隙を置いて接続された３次元構造を有する配位高分子金属錯体を骨格とし、上記間隙が上記支柱で区切られて成る細孔内に上記２個の水分子が内包されている水分子内包配位高分子金属錯体化合物が示されている。この化合物は、Ｃｕ（ＣｌＯ４）２・６Ｈ２ＯとＮａ２−２，３−ピラジンジカルボキシレートとをピラジン水溶液中で混合して反応させることで生成されている。細孔内に２個の水分子を内包したことで、常温でのプロトン伝導性を安定して得ることができるが、プロトン伝導性を更に向上させることはできなかった。 In contrast, in Non-Patent Document 1, one unit is [Cu 2 (C 6 H 2 N 2 O 4 ) 2 (C 4 H 4 N 2). 2 ) 2 having a composition represented by 2H 2 O, and a two-dimensional structure composed of the Cu element and pyrazine-2,3-dicarboxylate connected to each other with a pillar composed of pyrazine with a gap therebetween 3 A water molecule-encapsulated coordination polymer metal complex compound in which a coordination polymer metal complex having a dimensional structure is used as a skeleton, and the two water molecules are encapsulated in pores in which the gap is divided by the support columns. It is shown. This compound is produced by mixing and reacting Cu (ClO 4 ) 2 .6H 2 O and Na 2 -2,3-pyrazine dicarboxylate in an aqueous pyrazine solution. By enclosing two water molecules in the pores, proton conductivity at room temperature can be stably obtained, but proton conductivity could not be further improved.
本発明は、室温におけるプロトン伝導性を高めた水分子内包配位高分子金属錯体化合物を提供することを目的とする。 An object of the present invention is to provide a water molecule inclusion coordination metal-metal complex compound having improved proton conductivity at room temperature.
上記の目的を達成するために、第１発明によれば、１ユニットが[ＭＡ・２｛(Ｃ４Ｈ２Ｎ２)−(ＣＯＯＨ)２｝]・ｎＨ２Ｏで表わされる組成を有し、平面４配位構造を取る金属イオンＭＡと、２，３−ピラジンジカルボン酸と、結晶水としての水分子とから成る水分子内包１次元鎖状配位高分子金属錯体化合物が提供される。 In order to achieve the above object, according to the first invention, one unit has a composition represented by [MA · 2 {(C 4 H 2 N 2 ) — (COOH) 2 }] · nH 2 O. There is provided a water molecule-encapsulating one-dimensional chain coordination polymer metal complex compound comprising a metal ion MA having a planar four-coordinate structure, 2,3-pyrazinedicarboxylic acid, and water molecules as crystal water.
更に、第２発明によれば、１ユニットが[ＭＢ・２｛(Ｃ４Ｈ２Ｎ２)−(ＣＯＯＨ)２｝・２Ｈ２Ｏ〕・Ｈ２Ｏで表わされる組成を有し、６配位八面体構造を取る金属イオンＭＢと、２，３−ピラジンジカルボン酸と、配位子としての水分子および細孔内の水分子とから成る水分子内包３次元配位高分子金属錯体化合物が提供される。 Further, according to the second invention, one unit has a composition represented by [MB · 2 {(C 4 H 2 N 2 ) — (COOH) 2 } · 2H 2 O] · H 2 O, A water molecule-encapsulating three-dimensional coordination polymer metal complex compound comprising a metal ion MB having a octahedral structure, 2,3-pyrazinedicarboxylic acid, a water molecule as a ligand, and a water molecule in a pore. Provided.
第１発明の水分子内包１次元鎖状配位高分子金属錯体化合物は、結晶水として内包する水分子によりプロトン伝導性を有する。 The water molecule-encapsulating one-dimensional chain coordination polymer metal complex compound of the first invention has proton conductivity due to water molecules encapsulated as crystal water.
第２発明の水分子内包３次元配位高分子金属錯体化合物は、配位子としての水分子および細孔内の水分子を内包することにより更に高いプロトン伝導性を有する。 The water molecule-encapsulating three-dimensional coordination polymer metal complex compound of the second invention has higher proton conductivity by encapsulating water molecules as ligands and water molecules in pores.
〔実施形態１〕
図１に、第１発明による１次元鎖状配位高分子金属錯体化合物の構造例を示す。平面４配位金属イオンＭＡとしてＰｄを用いた場合を示した。同図は上記化合物の１ユニット分を示したものであり、４配位のＰｄイオンを中心にして両側に２，３−ピラジンジカルボン酸がイオン結合しており、更に各２，３−ピラジンジカルボン酸の他端にＰｄイオンが結合する。この結合サイクルを繰返して１次元鎖状構造の配位高分子金属錯体化合物が構成される。金属イオンＭＡ周りはトランス型をとっており、上記の１次元鎖状化合物間に水分子（図示せず）が結晶水として取り込まれており、これがプロトン伝導性が付与される。
Embodiment 1
FIG. 1 shows a structural example of a one-dimensional chain coordination polymer metal complex compound according to the first invention. The case where Pd is used as the planar four-coordinate metal ion MA is shown. This figure shows one unit of the above compound, and 2,3-pyrazinedicarboxylic acid is ion-bonded on both sides around the 4-coordinate Pd ion, and each 2,3-pyrazinedicarboxylic acid is further bonded. Pd ions are bonded to the other end of the acid. This bonding cycle is repeated to form a coordination polymer metal complex compound having a one-dimensional chain structure. Around the metal ion MA is in a trans form, and water molecules (not shown) are taken in as crystal water between the above one-dimensional chain compounds, and this imparts proton conductivity.
平面４配位金属イオンＭＡは、Ｃｏ(II)、Ｎｉ(II)、Ｃｕ(II)、Ｒｈ(I)、Ｐｄ(II)、Ｐｔ(II)から成る群から選択することができる。 The planar four-coordinate metal ion MA can be selected from the group consisting of Co (II), Ni (II), Cu (II), Rh (I), Pd (II), Pt (II).
〔実施形態２〕
図２に、第２発明による３次元配位高分子金属錯体化合物の構造例を示す。６配位八面体構造を取る金属イオンＭＢとしてＣｏを用いた場合を示した。同図は上記化合物の１ユニット分を示したものであり、６配位のＣｏイオンを中心にして、左右両側には２，３−ピラジンジカルボン酸が、上下両側には水分子がそれぞれイオン結合しており、更に下部に示したようにフリーの水分子１個を細孔（図示せず）内に内包している。細孔は、このユニットが多数結合した３次元構造中の各ユニット間の間隙である。
[Embodiment 2]
FIG. 2 shows a structural example of the three-dimensional coordination polymer metal complex compound according to the second invention. The case where Co is used as the metal ion MB having a six-coordinate octahedral structure is shown. The figure shows one unit of the above compound, with 2,3-pyrazinedicarboxylic acid on the left and right sides, and water molecules on the top and bottom sides, centered on the 6-coordinate Co ion. Furthermore, as shown in the lower part, one free water molecule is included in the pores (not shown). A pore is a gap between units in a three-dimensional structure in which a large number of units are bonded.
図３は、図２の３次元配位高分子金属錯体化合物を単結晶Ｘ線構造解析して得られた画像である。すなわち解析対象は、１ユニットが[Ｃｏ・２｛(Ｃ４Ｈ２Ｎ２)−(ＣＯＯＨ)２｝・２Ｈ２Ｏ〕・Ｈ２Ｏで表わされる組成を有する。Ｃｏイオン（図中、斑点模様で示した６配位部分）、Ｏ（斜線ハッチング部分）、Ｎ（クロスハッチング部分）が表示されている。本図では必ずしも明瞭ではないが、Ｃｏイオンの配位子の一部を成す水分子と細孔内の水分子とが水素結合（破線）して３次元構造を形成している。 FIG. 3 is an image obtained by analyzing a single crystal X-ray structure of the three-dimensional coordination polymer metal complex compound of FIG. In other words, the analysis target has a composition in which one unit is represented by [Co · 2 {(C 4 H 2 N 2 ) − (COOH) 2 } · 2H 2 O] · H 2 O. Co ions (six-coordinate portion indicated by a spot pattern in the figure), O (hatched hatched portion), and N (cross-hatched portion) are displayed. Although it is not necessarily clear in this figure, the water molecule which forms a part of the Co ion ligand and the water molecule in the pore form a hydrogen bond (broken line) to form a three-dimensional structure.
このように、配位子としての水分子と細孔内の水分子とが水素結合により３次元構造を形成しているため、Grotthus機構等により更にプロトン伝導性が向上する。Grotthus機構は、電解質溶液中に電流が流れるのは、電場の影響で水分子が正に荷電した水素と負に荷電した酸素とに分解し、直ちに再結合するという現象が電極面を除いて連続的に起きるという機構である。 Thus, since the water molecule as the ligand and the water molecule in the pore form a three-dimensional structure by hydrogen bonding, proton conductivity is further improved by the Grothus mechanism or the like. In the Grotthus mechanism, current flows in the electrolyte solution because the electric field affects the water molecules to decompose into positively charged hydrogen and negatively charged oxygen, and immediately recombine except for the electrode surface. It is a mechanism that happens automatically.
６配位八面体構造を取る金属イオンＭＢは、Ｔｉ(II)、Ｔｉ(III)、Ｔｉ(IV)、Ｃｒ(II)、Ｃｒ(III)、Ｍｎ(II)、Ｍｎ(III)、Ｍｎ(IV)、Ｆｅ(II)、Ｆｅ(III)、Ｃｏ(II)、Ｃｏ(III)、Ｎｉ(II)、Ｃｕ(II)、Ｒｕ(II)、Ｒｕ(III)、Ｒｕ(IV)から成る群から選択することができる。 Metal ions MB having a hexacoordinate octahedral structure are Ti (II), Ti (III), Ti (IV), Cr (II), Cr (III), Mn (II), Mn (III), Mn ( IV), Fe (II), Fe (III), Co (II), Co (III), Ni (II), Cu (II), Ru (II), Ru (III), Ru (IV) You can choose from.
図２、３に示した第２発明による水分子内包３次元配位高分子金属錯体化合物を下記の条件および手順により合成した。６配位八面体構造を取る金属イオンＭＢとしてコバルトを用いた。 A water molecule-encapsulating three-dimensional coordination polymer metal complex compound according to the second invention shown in FIGS. 2 and 3 was synthesized under the following conditions and procedures. Cobalt was used as a metal ion MB having a six-coordinate octahedral structure.
（１）塩化コバルト(II)六水和物を水５ｍｌに溶解させる（溶液Ａ）。 (1) Cobalt chloride (II) hexahydrate is dissolved in 5 ml of water (solution A).
（２）２，３−ピラジンジカルボン酸水溶液を水５ｍｌに溶解させる（溶液Ｂ）。 (2) A 2,3-pyrazinedicarboxylic acid aqueous solution is dissolved in 5 ml of water (solution B).
（３）溶液Ａに溶液Ｂを加えて室温で１０分攪拌する。 (3) Add Solution B to Solution A and stir at room temperature for 10 minutes.
（４）室温にて放置し、橙色結晶を得る。 (4) Leave at room temperature to obtain orange crystals.
得られた橙色結晶について単結晶Ｘ線構造解析を行なった結果、コバルト、２，３−ピラジンジカルボキシレート、水分子から成る化合物となっていることが分かった（図２）。その結晶内に水分子が取り込まれており、配位子の水分子と結晶水の水分子が水素結合により連結して３次元構造体を形成している（図３）。 As a result of single crystal X-ray structural analysis of the obtained orange crystals, it was found that the orange crystals were a compound composed of cobalt, 2,3-pyrazine dicarboxylate, and water molecules (FIG. 2). Water molecules are taken into the crystals, and the water molecules of the ligand and the water molecules of the crystal water are connected by hydrogen bonds to form a three-dimensional structure (FIG. 3).
この場合、コバルトイオンと配位子２，３−ピラジンジカルボン酸から成る１次元の鎖状化合物が形成されるが、更にコバルトイオンの配位子として２個の水分子が存在しており、これが結晶水として存在する１個の水分子と水素結合していることが分かった。その結果、水素結合ネットワークにより３次元構造体が形成されている。 In this case, a one-dimensional chain compound consisting of cobalt ions and the ligand 2,3-pyrazinedicarboxylic acid is formed, but there are two water molecules as cobalt ion ligands. It was found to be hydrogen-bonded with one water molecule present as crystal water. As a result, a three-dimensional structure is formed by the hydrogen bond network.
本実施例では、上記（１）の操作において６配位八面体構造を取る金属イオンとして用いるコバルト源として塩化コバルト(II)を用いたが、規定の選択範囲内の金属種を用いる場合には、その金属源としてはその金属の塩を用いることができる。 In this example, cobalt (II) chloride was used as a cobalt source used as a metal ion having a six-coordinate octahedral structure in the above operation (1). However, when a metal species within a specified selection range is used. As the metal source, a salt of the metal can be used.
また、上記（１）の操作において平面４配位構造を取る金属イオンの金属塩を用いることにより、第１発明による１次元鎖状配位高分子錯体化合物を合成することができる。 In addition, the one-dimensional chain coordination polymer complex compound according to the first invention can be synthesized by using a metal salt of a metal ion having a planar four-coordinate structure in the operation (1).
本発明によれば、室温におけるプロトン伝導性を高めた水分子内包配位高分子金属錯体化合物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the water molecule inclusion coordination polymer metal complex compound which improved the proton conductivity in room temperature is provided.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007016749A JP4882762B2 (en) | 2007-01-26 | 2007-01-26 | Water molecule inclusion coordination polymer metal complex compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007016749A JP4882762B2 (en) | 2007-01-26 | 2007-01-26 | Water molecule inclusion coordination polymer metal complex compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008184480A JP2008184480A (en) | 2008-08-14 |
| JP4882762B2 true JP4882762B2 (en) | 2012-02-22 |
Family
ID=39727735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007016749A Expired - Fee Related JP4882762B2 (en) | 2007-01-26 | 2007-01-26 | Water molecule inclusion coordination polymer metal complex compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4882762B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10376868B2 (en) | 2015-02-17 | 2019-08-13 | Lg Chem, Ltd. | Linear inorganic coordination polymer, metal complex compound, and metal nanostructure and catalyst composition comprising the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114373992B (en) * | 2022-01-25 | 2024-08-30 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device, and electronic device |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3746321B2 (en) * | 1996-02-28 | 2006-02-15 | 大阪瓦斯株式会社 | Gas storage organometallic complex, method for producing the same, gas storage device, and automobile equipped with gas storage device |
| JPH09324006A (en) * | 1996-06-05 | 1997-12-16 | Osaka Gas Co Ltd | Production of highly conductive polymer and organometallic complex for synthesizing the polymer |
| JP4129763B2 (en) * | 2002-06-26 | 2008-08-06 | 独立行政法人科学技術振興機構 | Anode electrode for fuel cell and manufacturing method thereof |
| JP4182395B2 (en) * | 2002-06-26 | 2008-11-19 | 独立行政法人科学技術振興機構 | Proton exchange membrane production method |
| JP4217776B2 (en) * | 2002-12-18 | 2009-02-04 | 国立大学法人京都大学 | Method for maintaining alignment of gas molecules |
| JP4578063B2 (en) * | 2003-04-25 | 2010-11-10 | 進 北川 | Selective adsorbent for isoprene gas, process for producing the same, and method for separating isoprene gas |
| JP5099614B2 (en) * | 2005-06-09 | 2012-12-19 | 公立大学法人横浜市立大学 | Novel metal carboxylate complex and gas storage agent comprising the same |
| JP2007204446A (en) * | 2006-02-03 | 2007-08-16 | Showa Denko Kk | Metal complex and method for recovering rare gas by using the same |
-
2007
- 2007-01-26 JP JP2007016749A patent/JP4882762B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10376868B2 (en) | 2015-02-17 | 2019-08-13 | Lg Chem, Ltd. | Linear inorganic coordination polymer, metal complex compound, and metal nanostructure and catalyst composition comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008184480A (en) | 2008-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Recent progress in metal–organic frameworks (MOFs) for electrocatalysis | |
| Li et al. | Metal–organic framework containing planar metal-binding sites: efficiently and cost-effectively enhancing the kinetic separation of C2H2/C2H4 | |
| Wang et al. | Construction and application of base-stable MOFs: a critical review | |
| Yang et al. | Ligand-directed conformational control over porphyrinic zirconium metal–organic frameworks for size-selective catalysis | |
| Gu et al. | Iron-based metal–organic framework system as an efficient bifunctional electrocatalyst for oxygen evolution and hydrogen evolution reactions | |
| Liang et al. | Effective approach to promoting the proton conductivity of metal–organic frameworks by exposure to aqua–ammonia vapor | |
| Oshio et al. | Cyanide‐Bridged Fe− Fe and Fe− Co Molecular Squares: Structures and Electrochemistry of [Fe4II (μ‐CN) 4 (bpy) 8](PF6) 4⋅ 4 H2O,[Fe2IICo2II (μ‐CN) 4 (bpy) 8](PF6) 4⋅ 3 CHCl3⋅ 2 CH3CN, and [Fe2IICo2III (μ‐CN) 4 (bpy) 8](PF6) 6⋅ 2 CHCl3⋅ 4 CH3NO2 | |
| Badiei et al. | Cp* Co (III) catalysts with proton-responsive ligands for carbon dioxide hydrogenation in aqueous media | |
| Eddaoudi et al. | Modular chemistry: secondary building units as a basis for the design of highly porous and robust metal− organic carboxylate frameworks | |
| Chen et al. | Nanostructured Cobalt‐Based Electrocatalysts for CO2 Reduction: Recent Progress, Challenges, and Perspectives | |
| Qi et al. | Single Metal–Organic Cage Decorated with an Ir (III) Complex for CO2 Photoreduction | |
| Thuery et al. | Uranyl and uranyl–3d block cation complexes with 1, 3-adamantanedicarboxylate: crystal structures, luminescence, and magnetic properties | |
| Zhou et al. | New metal–organic frameworks based on 2, 5-thiophenedicarboxylate and pyridine-or imidazole-based spacers: syntheses, topological structures, and properties | |
| Wu et al. | All roads lead to Rome: An energy-saving integrated electrocatalytic CO2 reduction system for concurrent value-added formate production | |
| Du et al. | Two 2D layered P4Mo6 clusters with potential bifunctional properties: proton conduction and CO2 photoreduction | |
| Chen et al. | Robust Anionic LnIII–Organic Frameworks: Chemical Fixation of CO2, Tunable Light Emission, and Fluorescence Recognition of Fe3+ | |
| Tian et al. | A series of organopolymolybdate polymers linked by dual fuses: metal–organic moiety and organic ligand through Mo–N bonds | |
| Kong et al. | Vanadium-based trimetallic metal-organic-framework family as extremely high-performing and ultrastable electrocatalysts for water splitting | |
| Konavarapu et al. | Isostructural NiII Metal–Organic Frameworks (MOFs) for Efficient Electrocatalysis of Oxygen Evolution Reaction and for Gas Sorption Properties | |
| Banerjee et al. | Design and synthesis of mixed valent coordination networks containing pyridine appended terpyridyl, halide, and dicarboxylates | |
| Ibrahim et al. | A trinuclear cobalt-based coordination polymer as an efficient oxygen evolution electrocatalyst at neutral pH | |
| Zhu et al. | Continuously producing highly concentrated and pure acetic acid aqueous solution via direct electroreduction of CO2 | |
| JP4882762B2 (en) | Water molecule inclusion coordination polymer metal complex compound | |
| Diyali et al. | Coordination-driven electrocatalysts as an evolving wave of enthusiasm for sustainable hydrogen production | |
| Sun et al. | {Cu8} cluster-sandwiched polyoxotungstates and their polymers: Syntheses, structures, and properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20091210 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110310 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110405 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110520 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20111108 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111121 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141216 Year of fee payment: 3 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4882762 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141216 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |