JP2002255518A - Production method for fullerene selectively including isotope atom by ion implantation method - Google Patents

Production method for fullerene selectively including isotope atom by ion implantation method

Info

Publication number
JP2002255518A
JP2002255518A JP2001054344A JP2001054344A JP2002255518A JP 2002255518 A JP2002255518 A JP 2002255518A JP 2001054344 A JP2001054344 A JP 2001054344A JP 2001054344 A JP2001054344 A JP 2001054344A JP 2002255518 A JP2002255518 A JP 2002255518A
Authority
JP
Japan
Prior art keywords
fullerene
isotope
ion implantation
target
ion
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
Application number
JP2001054344A
Other languages
Japanese (ja)
Other versions
JP4783509B2 (en
Inventor
Satoshi Watanabe
智 渡辺
Noriko Ishioka
典子 石岡
Toshiaki Sekine
俊明 関根
Akihiko Cho
明彦 長
Mitsuo Koizumi
光生 小泉
Hisakazu Muramatsu
久和 村松
Haruhiko Shimomura
晴彦 下村
Hirosuke Yoshikawa
広輔 吉川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Atomic Energy Agency
Original Assignee
Japan Atomic Energy Research Institute
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Japan Atomic Energy Research Institute filed Critical Japan Atomic Energy Research Institute
Priority to JP2001054344A priority Critical patent/JP4783509B2/en
Publication of JP2002255518A publication Critical patent/JP2002255518A/en
Application granted granted Critical
Publication of JP4783509B2 publication Critical patent/JP4783509B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Carbon And Carbon Compounds (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a method by which a radioactive isotope is included into fullerene by an ion implantation method. SOLUTION: The production method for fullerene including a specific isotope such as a radio active isotope is a method implanting the isotope using fullerene or a fullerene derivative as a target and an ion injector equipped with a mass spectrometry magnet.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】この発明は、放射性同位元素
等をフラーレンに内包させることに関するものであり、
同位元素内包フラーレンを製造するためにイオン注入法
を用いることを特徴とするものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to encapsulating radioisotopes and the like in fullerenes,
The method is characterized by using an ion implantation method for producing an isotope-encapsulated fullerene.

【0002】[0002]

【従来の技術】イオン注入法を用いた内包フラーレンの
製造方法としては、Li等のアルカリ元素内包フラーレン
(Tellgmann R. et al., Nature 382, 407-408 (199
6)、N内包フラーレン(Weidinger A. et al., Appl. P
hys. A 66, 287-292 (1998))およびHe、Ne内包フラー
レン(Shimshi R. et al., J. Am. Chem. Soc. 119, 11
63-1164 (1997))などが報告されている。これらはすべ
て、非同位元素選択的内包フラーレンに関した製造方法
である。また、キセノンの放射性同位体であるXe-127を
内包したフラーレンの製造方法は、127I(d, 2n) 127Xe
反応における反挑エネルギーを利用したもの(Ohtsuki
T. et al., Physical Review Letters 81,967-970 (199
8) )が報告されている。
2. Description of the Related Art As a method for producing an endohedral fullerene using an ion implantation method, an alkali element endohedral fullerene such as Li (Tellgmann R. et al., Nature 382, 407-408 (199)
6), N-encapsulated fullerene (Weidinger A. et al., Appl. P
hys. A 66, 287-292 (1998)) and He and Ne endohedral fullerenes (Shimshi R. et al., J. Am. Chem. Soc. 119, 11).
63-1164 (1997)). These are all production methods related to non-isotope-selective endohedral fullerenes. In addition, the method for producing fullerene containing Xe-127, a radioisotope of xenon, is described as 127 I (d, 2n) 127 Xe
Using the energy of counter-challenge in the reaction (Ohtsuki
T. et al., Physical Review Letters 81, 967-970 (199
8)) has been reported.

【0003】しかし、核反応を用いた場合、目的以外の
放射性同位元素内包フラーレンが生成する可能性があ
る。さらに、目的の同位元素を炭素棒電極に含ませてお
き、アーク放電法により同位元素内包フラーレンを製造
する方法が報告されている(Ambe F., J. Radioanal. N
ucl. Chem. 243, 21-25 (2000) )。しかし、この方法
で作られた金属内包フラーレンのフラーレン種は、多種
類生成してしまい、任意のフラーレン種の内包フラーレ
ンを作ることができない。
[0003] However, when a nuclear reaction is used, there is a possibility that an undesired radioisotope-encapsulated fullerene is generated. Further, a method has been reported in which a target isotope is contained in a carbon rod electrode and an isotope-encapsulated fullerene is produced by an arc discharge method (Ambe F., J. Radioanal.
ucl. Chem. 243, 21-25 (2000)). However, many kinds of fullerene species of metal-encapsulated fullerenes produced by this method are generated, and it is not possible to produce endohedral fullerenes of any type.

【0004】[0004]

【発明が解決しようとする課題】従来の技術として、イ
オン注入によるLi、N、HeおよびNe内包フラーレンの製
造方法が報告されているが、これらはすべて非同位元素
選択的なものである。また、核反応を用いた放射性同位
元素内包フラーレンの製造方法が報告されているが、目
的以外の同位元素内包フラーレンが生成してしまい、単
一の同位元素内包フラーレンを作ることができない。
As a conventional technique, a method for producing Li, N, He and Ne-encapsulated fullerenes by ion implantation has been reported, but these are all non-isotopic selective. In addition, a method for producing a radioisotope-encapsulated fullerene using a nuclear reaction has been reported. However, a non-target isotope-encapsulated fullerene is generated, and a single isotope-encapsulated fullerene cannot be produced.

【0005】さらに、アーク放電法を用いた同位元素内
包フラーレンの製造方法が報告されているが、これは任
意のフラーレン種(C60、C70、C82等、フラーレン誘導
体を含めてその他多数のフラーレン種の存在が明らかに
なっている)の内包フラーレンが生成できない。そこ
で、本発明はこれらの問題を解決するために創案された
ものである。
Further, a method for producing an isotope-encapsulated fullerene by using an arc discharge method has been reported. However, it has been reported that any of a variety of fullerene species (such as C 60 , C 70 , C 82, etc. (The existence of fullerene species has been clarified.) Thus, the present invention has been devised to solve these problems.

【0006】[0006]

【課題を解決するための手段】本発明は、単一の同位元
素のイオン注入が可能なイオン注入器を用いることによ
り、目的以外の同位元素を含まない内包フラーレンを製
造できる。さらに、イオン注入のターゲットとして任意
のフラーレン種を選べることから、任意のフラーレン種
の内包フラーレンを製造することができる。
According to the present invention, an endohedral fullerene containing no isotope other than the intended one can be produced by using an ion implanter capable of implanting a single isotope. Furthermore, since an arbitrary fullerene species can be selected as a target for ion implantation, an endohedral fullerene of an arbitrary fullerene species can be manufactured.

【0007】[0007]

【発明の実施の形態】イオン注入器によるイオン注入に
ついて 本発明では、単一の同位元素をイオン注入するために、
質量分析マグネットを備えたイオン注入器(図1)を用
いる。以下にそのイオン注入器の概要を示す。イオン注
入器のターゲットチャンバー3内にターゲット4を設置し
て真空中でイオン注入を行う。このとき、イオン源1で
生成された種々のイオンはイオンビームとして質量分析
マグネット2に運ばれる。ここでイオンビームの質量分
離が行われるため、ターゲット4には目的の同位元素イ
オンビーム5だけがイオン注入される。
DESCRIPTION OF THE PREFERRED EMBODIMENTS For ion implantation by an ion implanter
In the present invention, in order to implant a single isotope,
An ion implanter (FIG. 1) equipped with a mass analysis magnet is used. The outline of the ion implanter is shown below. The target 4 is set in the target chamber 3 of the ion implanter, and ion implantation is performed in a vacuum. At this time, various ions generated by the ion source 1 are carried to the mass analysis magnet 2 as an ion beam. Here, since mass separation of the ion beam is performed, only the target isotope ion beam 5 is ion-implanted into the target 4.

【0008】ターゲットについて イオン注入のターゲットとしては、フラーレン誘導体も
含めて任意のフラーレン種を用いる。また、本発明で用
いるイオン注入器は特定の同位元素を質量分離するた
め、通常40 keVで稼動させるが、同位元素内包フラーレ
ンを製造する上で、同位元素イオンの入射エネルギーと
しては高すぎるため、そのイオンの減速が必要である。
そこで、以下に示す減速法の異なる2つの方法を用い
る。 (1)フラーレンと減速材(CsI等の粉末)を任意の割
合で混合してペレット状のターゲットを作成し、これに
同位元素のイオン注入を行う。 (2)金属箔にフラーレンを蒸着して薄膜ターゲットを
作成する。この薄膜ターゲットの前面に減速装置として
+の電圧をかけたスリットを設置して同位元素のイオン
注入を行う。以下に放射性同位元素であるXe-133を例
にあげ、本発明の具体的な実施例を示す。
[0008] As the target for ion implantation, any fullerene species including a fullerene derivative is used. In addition, the ion implanter used in the present invention is usually operated at 40 keV for mass separation of a specific isotope, but in producing an isotope-encapsulated fullerene, the incident energy of the isotope ion is too high. It is necessary to slow down the ions.
Therefore, two different methods of deceleration described below are used. (1) Fullerene and a moderator (powder such as CsI) are mixed at an arbitrary ratio to prepare a pellet-shaped target, and isotope ion implantation is performed on the target. (2) Fullerene is deposited on a metal foil to form a thin film target. In front of this thin film target as a reduction gear
A slit to which a voltage of + is applied is installed to perform ion implantation of isotopes. Hereinafter, specific examples of the present invention will be described by taking Xe-133 as a radioisotope as an example.

【0009】[0009]

【実施例】133Xeガス200 MBqを真空ラインにより3.8リ
ットル試料ボンベに移送した。質量分離における質量の
指標として約3 cm3129Xe濃縮同位体も同じボンベに充
填した。このボンベをイオン注入器のNielsen型イオン
源に接続し、40 keVでターゲットであるフラーレンに
133Xeをイオン注入した。ターゲットは2種類の方法で作
成した。1つ目は、CsCl(0.8g)をサポートとし、50 m
gのフラーレン(C60)と18 mgのCsIを混合したものを加
圧成型し、ペレット(直径18 mm)を作製した。2つ目
は、蒸着装置を用いてNi箔(25×25 mm)にフラーレン
(C60)を約1.5 μm蒸着したものをターゲットとし
た。このNi箔蒸着ターゲットを用いる場合、ターゲット
の前面に減速装置として+の電圧をかけたスリットを設
置して133Xe+イオンを0.5〜3 keVに減速させた。イオン
注入後、これらのターゲットをo-ジクロロベンゼンに溶
解し、高速液体クロマトグラフィー(HPLC)によりフラ
ーレンを分析した。また、溶出液を分取して、Xe-133の
放射能を測定した。HPLCによるフラーレンのピークと溶
出液中のXe-133のピークが一致したことから、Xe-133内
包フラーレンが生成していることが確認された。また、
ターゲットにイオン注入されたすべてのXe-133の放射能
に対するフラーレンに内包されたXe-133の放射能の割合
を捕獲確率として算出した。
EXAMPLE 200 MBq of 133 Xe gas was transferred to a 3.8 liter sample cylinder by a vacuum line. Approximately 3 cm 3 of 129 Xe enriched isotope was also loaded into the same cylinder as an indicator of mass in mass separation. This cylinder was connected to the Nielsen-type ion source of the ion implanter, and was connected to the target fullerene at 40 keV.
133 Xe was ion-implanted. Targets were created in two different ways. The first is with CsCl (0.8g) support, 50m
A mixture of g fullerene (C 60 ) and 18 mg CsI was molded under pressure to produce a pellet (diameter: 18 mm). The second was a target obtained by depositing fullerene (C 60 ) on a Ni foil (25 × 25 mm) with a thickness of about 1.5 μm using a deposition apparatus. When this Ni foil deposition target was used, a slit with a + voltage was installed as a speed reducer in front of the target to reduce 133 Xe + ions to 0.5 to 3 keV. After ion implantation, these targets were dissolved in o-dichlorobenzene, and fullerene was analyzed by high performance liquid chromatography (HPLC). Further, the eluate was fractionated and the radioactivity of Xe-133 was measured. Since the peak of fullerene by HPLC coincided with the peak of Xe-133 in the eluate, it was confirmed that Xe-133-encapsulated fullerene was generated. Also,
The ratio of the radioactivity of Xe-133 contained in fullerene to the radioactivity of all Xe-133 ion-implanted into the target was calculated as the capture probability.

【数1】 上述した条件で作成したペレットを用いた時の捕獲確率
は、現段階で最大値(0.28%)を示した。なお、ターゲ
ットであるフラーレンからのXe-133内包フラーレンの単
離は、HPLCを用いることにより(DiCamillo B. A. et a
l., J. Phys. Chem. 100(22), 9197-9201 (2000)) 原理
的には可能である。また、ここではXe-133のイオン注
入の例を示したが、イオン化が可能な同位元素であれ
ば、原理的にはそれらすべての同位元素内包フラーレン
を本発明を用いて作ることができる。
(Equation 1) The capture probability when the pellets prepared under the above conditions were used showed the maximum value (0.28%) at this stage. The Xe-133-encapsulated fullerene was isolated from the target fullerene by HPLC (DiCamillo BA et a
l., J. Phys. Chem. 100 (22), 9197-9201 (2000)) It is possible in principle. Although an example of ion implantation of Xe-133 has been described here, all the isotope-encapsulated fullerenes can be made by using the present invention in principle, as long as the isotopes are ionizable.

【0010】[0010]

【発明の効果】本発明により、目的以外の同位元素を含
まず、かつ任意のフラーレン種の同位元素内包フラーレ
ンを作ることができる。さらに、作成した同位元素内包
フラーレンは核医学での利用の可能性がある。実施例の
Xe-133はβ-線放出核種であるため、Xe-133内包フラー
レンを癌に集まるような化学形に変換すれば、癌の治療
薬として利用できると考えられる。
According to the present invention, it is possible to produce an isotope-encapsulated fullerene of an arbitrary fullerene type which does not contain an isotope other than the intended one. Furthermore, the prepared isotope-encapsulated fullerenes may be used in nuclear medicine. Of the embodiment
Since Xe-133 is a β - ray emitting nuclide, it is considered that Xe-133-encapsulated fullerene can be used as a therapeutic agent for cancer if it is converted into a chemical form that condenses with cancer.

【図面の簡単な説明】[Brief description of the drawings]

【図1】 同位元素内包フラーレンを製造するためのイ
オン注入器を示した図である。
FIG. 1 is a diagram showing an ion implanter for producing an isotope-encapsulated fullerene.

【符号の説明】[Explanation of symbols]

1・・・・・・・・イオン源 2・・・・・・・・質量分析マグネット 3・・・・・・・・ターゲットチャンバー 4・・・・・・・・ターゲット 5・・・・・・・・目的の同位元素イオンビーム 1 ... Ion source 2 ... Magnet analysis magnet 3 ... Target chamber 4 ... Target 5 ... ... Isotope ion beam of interest

───────────────────────────────────────────────────── フロントページの続き (72)発明者 関根 俊明 群馬県高崎市綿貫町1233番地 日本原子力 研究所高崎研究所内 (72)発明者 長 明彦 群馬県高崎市綿貫町1233番地 日本原子力 研究所高崎研究所内 (72)発明者 小泉 光生 群馬県高崎市綿貫町1233番地 日本原子力 研究所高崎研究所内 (72)発明者 村松 久和 長野県長野市大字西長野6のロ 信州大学 内 (72)発明者 下村 晴彦 長野県長野市大字西長野6のロ 信州大学 内 (72)発明者 吉川 広輔 長野県長野市大字西長野6のロ 信州大学 内 Fターム(参考) 4G046 CB01 CC10  ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiaki Sekine 1233 Watanukicho, Takasaki City, Gunma Prefecture Inside the Japan Atomic Energy Research Institute Takasaki Research Institute (72) Inventor Nagaaki 1233 Watanukicho, Takasaki City, Gunma Prefecture Japan Atomic Energy Research Institute Takasaki Research Office (72) Inventor Mitsuo Koizumi 1233 Watanuki-cho, Takasaki City, Gunma Prefecture Japan Atomic Energy Research Institute Takasaki Research Institute (72) Inventor Hisakazu Muramatsu Shinano University, 6-figure Nishi-Nagano, Nagano City, Nagano Prefecture (72) Inventor Shimomura Haruhiko Nagano City, Nagano City, Oji Nishi-Nagano 6 Shinshu University (72) Inventor Kosuke Yoshikawa Nagano City, Nagano City, Oji Nishi-Nagano 6 Shinshu University F-term (reference) 4G046 CB01 CC10

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 質量分析マグネットを装備したイオン注
入器を用い、フラーレンおよびフラーレン誘導体をター
ゲットとして放射性同位元素等の特定同位元素をイオン
注入することを特徴とする原子内包フラーレンの製造方
法。
1. A method for producing an atom-encapsulated fullerene, which comprises ion-implanting a specific isotope such as a radioactive isotope using a fullerene and a fullerene derivative as a target by using an ion implanter equipped with a mass spectrometer magnet.
JP2001054344A 2001-02-28 2001-02-28 Method for producing xenon 133 endohedral fullerene by ion implantation Expired - Fee Related JP4783509B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2001054344A JP4783509B2 (en) 2001-02-28 2001-02-28 Method for producing xenon 133 endohedral fullerene by ion implantation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2001054344A JP4783509B2 (en) 2001-02-28 2001-02-28 Method for producing xenon 133 endohedral fullerene by ion implantation

Publications (2)

Publication Number Publication Date
JP2002255518A true JP2002255518A (en) 2002-09-11
JP4783509B2 JP4783509B2 (en) 2011-09-28

Family

ID=18914694

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2001054344A Expired - Fee Related JP4783509B2 (en) 2001-02-28 2001-02-28 Method for producing xenon 133 endohedral fullerene by ion implantation

Country Status (1)

Country Link
JP (1) JP4783509B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005053904A (en) * 2003-07-24 2005-03-03 Ideal Star Inc Fullerene and anticancer therapeutic agent
WO2005066385A1 (en) * 2004-01-06 2005-07-21 Ideal Star Inc. Ion implantation system and ion implantation system
WO2005090633A1 (en) * 2004-03-23 2005-09-29 Ideal Star Inc. Process for producing material film and material film production apparatus

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63304563A (en) * 1987-06-03 1988-12-12 Hitachi Ltd Ion implantation
JPH0613018A (en) * 1992-06-29 1994-01-21 Tokyo Electron Ltd Ion implantation device
JPH06184738A (en) * 1992-08-26 1994-07-05 Mitsubishi Electric Corp Formation of carbon thin film, its modifying method, electronic device formed by using this modifying method as well as x-ray multilayer film mirror and its production
JPH0765761A (en) * 1993-08-30 1995-03-10 Hitachi Ltd Thin film forming method and ion implanting method
JPH10283977A (en) * 1997-04-10 1998-10-23 Nissin Electric Co Ltd Ion implanting device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63304563A (en) * 1987-06-03 1988-12-12 Hitachi Ltd Ion implantation
JPH0613018A (en) * 1992-06-29 1994-01-21 Tokyo Electron Ltd Ion implantation device
JPH06184738A (en) * 1992-08-26 1994-07-05 Mitsubishi Electric Corp Formation of carbon thin film, its modifying method, electronic device formed by using this modifying method as well as x-ray multilayer film mirror and its production
JPH0765761A (en) * 1993-08-30 1995-03-10 Hitachi Ltd Thin film forming method and ion implanting method
JPH10283977A (en) * 1997-04-10 1998-10-23 Nissin Electric Co Ltd Ion implanting device

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005053904A (en) * 2003-07-24 2005-03-03 Ideal Star Inc Fullerene and anticancer therapeutic agent
WO2005066385A1 (en) * 2004-01-06 2005-07-21 Ideal Star Inc. Ion implantation system and ion implantation system
JP4769083B2 (en) * 2004-01-06 2011-09-07 株式会社イデアルスター Ion implantation method and ion implantation apparatus
WO2005090633A1 (en) * 2004-03-23 2005-09-29 Ideal Star Inc. Process for producing material film and material film production apparatus

Also Published As

Publication number Publication date
JP4783509B2 (en) 2011-09-28

Similar Documents

Publication Publication Date Title
Hofmann et al. The new element 111
Reifarth et al. Stellar neutron capture on promethium: implications for the s-process neutron density
Wexler et al. Dissociation of Methyl Bromide by Nuclear Isomeric Transition of 4.4‐hr Br80 m
Ratzel et al. Nucleosynthesis at the termination point of the s process
Pavetich et al. Interlaboratory study of the ion source memory effect in 36Cl accelerator mass spectrometry
Harvey NorthStar perspectives for actinium-225 production at commercial scale
Liu et al. Production of negatively charged radioactive ion beams
Dillmann et al. Determination of the stellar (n, γ) cross section of Ca 40 with accelerator mass spectrometry
JP2002255518A (en) Production method for fullerene selectively including isotope atom by ion implantation method
Köster et al. Off-line production of intense 7, 10Be+ beams
Imamura et al. Measurements of production cross sections of C and 26Al with high-energy neutrons up to En= 38 MeV by accelerator mass spectrometry
Fallis et al. Determination of the proton separation energy of Rh 93 from mass measurements
He et al. Measurement of 79Se and 64Cu with PXAMS
Suzuki et al. Performance of the new iodine-129 beamline at JAERI-AMS
Bacon et al. Atomic spectrometry update. Atomic mass spectrometry
He et al. Measurement of the cross-section of 14N (16O, α) 26Al with AMS
Da Cruz et al. Decay of 132 Cs and nuclear structure of 132 Xe
Takahashi et al. Isomer Re 1 8 8 m
Yin et al. Measurement of 151Sm with the HI-13 accelerator mass spectrometry system
Kosta et al. High energy photon activation
De Gerone et al. Commissioning of the Ion Implanter for the HOLMES Experiment
Dong et al. Measurement of ultra-low potassium contaminations with Accelerator Mass Spectrometry
Ma et al. Preliminary research on method of tree ring’s NE-OBT measurement using AMS
Stenström et al. The decay of neutron-deficient Er and Ho nucleides
Fisher et al. The Decay of the Isomeric State of 198Tl

Legal Events

Date Code Title Description
A711 Notification of change in applicant

Free format text: JAPANESE INTERMEDIATE CODE: A712

Effective date: 20060223

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20071113

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20100730

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20110310

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20110425

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: 20110615

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: 20110711

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20140715

Year of fee payment: 3

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

LAPS Cancellation because of no payment of annual fees