JP3141072B2 - Process for producing 2-iodine-2,3,3,3-tetrafluoropropionic acid fluoride and esters thereof - Google Patents
Process for producing 2-iodine-2,3,3,3-tetrafluoropropionic acid fluoride and esters thereofInfo
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- JP3141072B2 JP3141072B2 JP11054024A JP5402499A JP3141072B2 JP 3141072 B2 JP3141072 B2 JP 3141072B2 JP 11054024 A JP11054024 A JP 11054024A JP 5402499 A JP5402499 A JP 5402499A JP 3141072 B2 JP3141072 B2 JP 3141072B2
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- Japan
- Prior art keywords
- iodine
- reaction
- producing
- acid fluoride
- tetrafluoropropionic acid
- 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 - Lifetime
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐熱性、耐薬品性
を有するフッ素樹脂（含フッ素イオノマー）の製造のた
めの単量体として有用な２，３，３，３−トリフルオロ
アクリル酸の合成前駆体である２−ヨウ化−２，３，
３，３−テトラフルオロプロピオン酸フルオリド及びそ
のエステルの製造方法に関するものである。TECHNICAL FIELD The present invention relates to a 2,3,3,3-trifluoroacrylic acid useful as a monomer for producing a heat-resistant and chemical-resistant fluororesin (fluorine-containing ionomer). 2-iodide-2,3, a synthetic precursor
The present invention relates to a method for producing 3,3-tetrafluoropropionic acid fluoride and an ester thereof.
【０００２】[0002]
【従来の技術】フッ素樹脂は、耐熱性、耐薬品性で特徴
づけられる工業的に重要な高分子であるが、その側鎖中
にカルボキシル基やスルホン基などの官能基を含むもの
は含フッ素イオノマーとしてイオン交換膜や燃料電池の
隔膜などの用途を有している。含フッ素イオノマーの製
造のための単量体のなかでも、２，３，３−トリフルオ
ロアクリル酸誘導体は、重合部位である二重結合に直結
している炭素上に、官能基としてのカルボキシル基が結
合している最も基本的な単量体である。従って、従来よ
り、該２，３，３−トリフルオロアクリル酸誘導体より
成る単量体の合成には多くの研究がなされている。例え
ば、Eur．Pat．Appl．EP ２８７，００４によれば、ヘ
キサフルオロプロピレンを原料とし、これとハロゲンフ
ルオロサルフェイト〔化学式：ＸＯＳＯ2Ｆ（Ｘ＝Ｃ
ｌ，Ｂｒ，Ｉ）〕を反応させて、まず１：１付加体（化
学式：ＣＦ3ＣＦＸＣＦ2ＯＳＯ2Ｆ）を得た後、アルカ
リ金属フッ化物の存在下に脱フッ化スルフリル反応させ
ることにより、対応する２−ハロゲン化−２，３，３，
３−テトラフルオロプロピオン酸フルオリド〔化学式：
ＣＦ3ＣＦＸＣ（Ｏ）Ｆ（Ｘ＝Ｃｌ，Ｂｒ，Ｉ）〕を合
成している。２−ハロゲン化−２，３，３，３−テトラ
フルオロプロピオン酸フルオリドを原料とし、亜鉛と反
応させて脱ハロゲン化フッ素させることことにより、含
フッ素イオノマーの単量体となる２，３，３−トリフル
オロアクリル酸フルオリド(化学式：ＣＦ2=ＣＦＣ
（Ｏ）Ｆ）が合成できる。しかしながら、最初のヘキサ
フルオロプロピレンとハロゲンフルオロサルフェイトと
の１：１付加体の合成において、ハロゲンがヨウ素の場
合には、一方の反応原料であるヨウ化フルオロサルフェ
イト（ＩＯＳＯ2Ｆ）は不安定であるために、塩化フル
オロサルフェイト（ＣｌＯＳＯ2Ｆ）にヨウ素を添加す
るか、又はパイロジスルフリルフルオリド〔化学式：
（ＦＳＯ2Ｏ）2〕とヨウ素を反応させてｉｎｓｉｔｕに
ヨウ化フルオロサルフェイトを発生させることによりヘ
キサフルオロプロピレンとの反応に供している。しかし
ながら、この反応では、ハロゲンフルオロサルフェイト
（ＸＯＳＯ2Ｆ：Ｘ＝Ｃｌ，Ｂｒ，Ｉ）は強酸化剤のた
めに取り扱いには十分の注意が必要とされるなど反応の
スケールアップには難点がある。その他の合成方法とし
ては、ポリクロロポリフルオロプロペンを原料として用
いて、多段階の反応による合成法が知られている。例え
ば、パレッタ氏らは、１，１，２−トリクロロ−２，
３，３−トリフルオロプロペンを用いて、１）臭素との
反応による１：１付加体の合成（化学式：ＣＦ2ＣｌＣ
ＦＢｒＣｌ２Ｂｒ）、２）発煙硫酸による酸化反応によ
る酸クロリドへの変換（化学式：ＣＦ2ＣｌＣＦＢｒＣ
（Ｏ）Ｃｌ、３）フッ化アンチモンによるサンクロリド
からサンフルオリドへのフッ素化反応（化学式：ＣＦ2
ＣｌＣＦＢｒＣ（Ｏ）Ｆ）、の各反応を経て、最終的に
５）亜鉛を用いる脱臭素による二重結合の生成（化学
式：ＣＦ 2＝ＣＦＣ（Ｏ）Ｆ）により目的とする２，
３，３−トリフルオロアクリル酸誘導体の合成を行って
いる〔O．Paleta，A．Posta and Z．Novotva，Coll．Cz
ech．Chem．Comm．，33（1968）2970〕。しかしなが
ら、後者の方法では、合成に多段階の反応行程を必要と
するためにより簡便な合成方法の開発が求められてい
た。一方、ヘキサフルオロプロペンオキシドを原料とす
る反応として、例えば、ヨウ素化合物との求核的反応に
より、２−ヨウ化−２，３，３，３−テトラフルオロプ
ロピオン酸フルオリドを合成する試みがなされたが、望
ましい反応よりも、原料のヘキサフルオロプロペンオキ
シドの副反応が優先して起こるために、その合成には成
功していなかった〔R. O'B. Watts, C. G. Allison, K.
P. Barthold, and P. Tarrant, J. Fluorine Chem., 3
(1973/74) 7〕。2. Description of the Related Art Fluororesins are characterized by heat resistance and chemical resistance.
It is an industrially important polymer that can be attached to
Containing a functional group such as a carboxyl group or a sulfone group
Is a fluorine-containing ionomer for ion exchange membranes and fuel cells.
It has applications such as diaphragms. Production of fluorinated ionomer
Among the monomers for the production, 2,3,3-trifluoro
Polyacrylic acid derivative is directly connected to the double bond
Carboxyl group as a functional group
The most basic monomer that is combined. Therefore,
From the 2,3,3-trifluoroacrylic acid derivative
Much work has been done on the synthesis of these monomers. example
For example, Eur. Pat. Appl. According to EP 287,004,
Xafluoropropylene as a raw material,
Fluorosulfate [Chemical formula: XOSOTwoF (X = C
l, Br, I)] to form a 1: 1 adduct
Formula: CFThreeCFXCFTwoOSOTwoAfter obtaining F),
Defluoridation sulfuryl reaction in the presence of metal fluoride
By doing so, the corresponding 2-halogenated-2,3,3,
3-tetrafluoropropionic acid fluoride [chemical formula:
CFThreeCFXC (O) F (X = Cl, Br, I)]
Has formed. 2-halogenated-2,3,3,3-tetra
Using fluoropropionic acid fluoride as the raw material,
By reacting with dehalogenated fluorine.
2,3,3-Trifur which is a monomer of fluorine ionomer
Oroacrylic acid fluoride (chemical formula: CFTwo= CFC
(O) F) can be synthesized. However, the first hexa
With fluoropropylene and halogen fluorosulfate
In the synthesis of a 1: 1 adduct of
In this case, one of the reactants, fluorosulfur iodide
Ito (IOSO)TwoF) is unstable.
Oro Sulfate (ClOSOTwoF) Add iodine
Or pyrosulfurfuryl fluoride [chemical formula:
(FSOTwoO)Two] And iodine to react in situ
The generation of fluorosulfate iodide
It is used for the reaction with xafluoropropylene. However
While in this reaction, halogen fluorosulfate
(XOSOTwoF: X = Cl, Br, I) is a strong oxidant
Reaction requires careful attention to handle
There are drawbacks to scaling up. Other synthesis methods
Use polychloropolyfluoropropene as raw material
Thus, a synthesis method by a multi-step reaction is known. example
For example, Palletta and colleagues reported that 1,1,2-trichloro-2,
Using 3,3-trifluoropropene, 1) with bromine
Synthesis of 1: 1 adduct by reaction (chemical formula: CFTwoClC
FBrCl2Br), 2) By oxidation reaction with fuming sulfuric acid
Conversion to acid chloride (chemical formula: CFTwoClCFBrC
(O) Cl, 3) Sanchloride with antimony fluoride
Reaction of methane to sanfluoride (chemical formula: CFTwo
ClCFBrC (O) F), and finally,
5) Double bond formation by debromination using zinc (Chemical
Formula: CF Two= CFC (O) F)
Synthesis of 3,3-trifluoroacrylic acid derivative
[O. Paleta, A .; Posta and Z. Novotva, Coll. Cz
ech. Chem. Comm. , 33 (1968) 2970]. But
The latter method requires multi-step reaction steps for synthesis.
Development of a simpler synthesis method is required.
Was. On the other hand, hexafluoropropene oxide is used as a raw material.
Reaction, for example, a nucleophilic reaction with an iodine compound
From 2-iodine-2,3,3,3-tetrafluorop
Attempts have been made to synthesize lopionic acid fluoride, but
Hexafluoropropene ox
Since the side reaction of SID occurs preferentially,
R. O'B.Watts, C.G.Allison, K.
P. Barthold, and P. Tarrant, J. Fluorine Chem., 3
(1973/74) 7].
【０００３】[0003]
【発明が解決しようとする課題】本発明は、容易に入手
しうる原料を用いて製造することが可能であって、しか
も出来るだけ少ない反応行程で、かつ、収率良く２，
３，３，３−トリフルオロアクリル酸の前駆体の製造方
法を提供することをその課題とする。DISCLOSURE OF THE INVENTION The present invention can be produced using easily available raw materials, and has as few reaction steps as possible and in good yield.
An object of the present invention is to provide a method for producing a precursor of 3,3,3-trifluoroacrylic acid.
【０００４】[0004]
【課題を解決するための手段】本発明者は前記課題を解
決すべく鋭意研究を重ねた結果、工業的に大量に合成さ
れているヘキサフルオロプロペノキシドとの反応で、一
定の反応条件下にトリメチルシリルヨージドと反応させ
ることによりその課題を解決し得ることを見出し、この
知見に基づいて本発明を完成するに至った。即ち、本発
明によれば、下記式（１）Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, under certain reaction conditions, in the reaction with hexafluoropropenoxide which is industrially synthesized in large quantities. It has been found that the above problem can be solved by reacting the compound with trimethylsilyl iodide, and the present invention has been completed based on this finding. That is, according to the present invention, the following formula (1)
【化３】 ＣＦ3ＣＦＩＣ（Ｏ）Ｆ （１） で表される２−ヨウ化−２，３，３，３−テトラフルオ
ロプロピオン酸フルオリドを製造する方法において、ヘ
キサフルオロプロペンオキシドと、トリメチルシリルヨ
ージドとの反応で合成することを特徴とする２−ヨウ化
−２，３，３，３−テトラフルオロプロピオン酸フルオ
リドの製造方法が提供される。Embedded image In a method for producing 2-iodine-2,3,3,3-tetrafluoropropionic acid fluoride represented by CF 3 CFIC (O) F (1), hexafluoropropene oxide and trimethylsilyl iodide And a method for producing 2-iodine-2,3,3,3-tetrafluoropropionic acid fluoride, characterized by being synthesized by reacting with iodine.
【０００５】[0005]
【発明の実施の形態】本発明で一方の反応原料として用
いるヘキサフルオロプロペンオキシド（ＨＦＰＯ）は、
下記式（３）DETAILED DESCRIPTION OF THE INVENTION Hexafluoropropene oxide (HFPO) used as one reaction raw material in the present invention is:
The following equation (3)
【化４】 で表わされる化合物で、フッ素化化学工業分野でフッ素
樹脂（ＰＦＡ樹脂）の原料として大量に生産されてい
る。Embedded image Which is produced in large quantities as a raw material of a fluororesin (PFA resin) in the field of fluorinated chemical industry.
【０００６】本発明で他方の反応原料として用いるトリ
メチルシリルヨージド（ＴＭＳｉＩ）は、下記式（４）The trimethylsilyl iodide (TMSiI) used as the other reaction material in the present invention is represented by the following formula (4)
【化５】 （ＣＨ3）3ＳｉＩ （４） で表わされる化合物であり、市販薬品として容易に入手
することができる。Embedded image It is a compound represented by (CH 3 ) 3 SiI (4) and can be easily obtained as a commercial drug.
【０００７】本発明によれば、前記式（１）の化合物
は、前記式（３）のＨＦＰＯとＴＭＳｉＩとを反応させ
ることによって得ることができる。この場合の反応は次
式で表される。According to the present invention, the compound of the formula (1) can be obtained by reacting the HFPO of the formula (3) with TMSiI. The reaction in this case is represented by the following equation.
【化６】 Embedded image
【０００８】前記反応において、ＴＭＳｉＩの使用量
は、ＦＨＰＯ １モルに対し、１〜１．５モル、好まし
くは当モルである。その反応温度は１２０〜１８０℃、
好ましくは１４０〜１５０℃である。In the above reaction, the amount of TMSiI used is 1 to 1.5 mol, preferably equimolar, per 1 mol of FHPO. The reaction temperature is 120-180 ° C,
Preferably it is 140-150 degreeC.
【０００９】本発明によれば、前記一般式（２）の化合
物は、前記のようにして得られたＣＦ3ＣＦＩＣ（Ｏ）
Ｆにアルキルアルコールをエステル化反応させることに
より得ることができる。前記アルキルアルコールは、下
記一般式（５）で表わされる。According to the present invention, the compound of the general formula (2) is obtained by using the CF 3 CFIC (O) obtained as described above.
It can be obtained by subjecting F to an alkyl alcohol esterification reaction. The alkyl alcohol is represented by the following general formula (5).
【化７】Ｒ1ＯＨ （５） 前記式中、Ｒ1は炭素数１〜５、好ましくは１〜３のア
ルキル基を示す。この場合のアルキル基は、ハロゲン原
子、例えば、フッ素原子や塩素原子、ヨウ素原子を含有
することができる。R 1 OH (5) In the above formula, R 1 represents an alkyl group having 1 to 5, preferably 1 to 3 carbon atoms. In this case, the alkyl group may contain a halogen atom, for example, a fluorine atom, a chlorine atom, or an iodine atom.
【００１０】[0010]
【発明の効果】本発明によれば、ヘキサフルオロプロペ
ンオキシド（ＨＦＰＯ）とのトリメチルシリルヨージド
とを加熱反応させるという一段階の反応により、含フッ
素イオノマーを得るための単量体の原料となる２−ヨウ
化−２，３，３，３−テトラフルオロプロピオン酸フル
オリドが収率よく合成できる。また、このものをアルキ
ルアルコールと反応させることにより、そのエステルを
得ることができる。According to the present invention, a one-step reaction of heating hexafluoropropene oxide (HFPO) with trimethylsilyl iodide is used as a raw material of a monomer for obtaining a fluorine-containing ionomer. -Iodide-2,3,3,3-tetrafluoropropionic acid fluoride can be synthesized in good yield. The ester can be obtained by reacting this with an alkyl alcohol.
【００１１】[0011]
【実施例】次に、本発明を実施例によりさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００１２】実施例１ 反応容器としてステンレス製ミニバルブの付属した、容
量が１００ｍｌのステンレス反応管を用いた。また、反
応管には攪拌を効果的にするためニッケル製ボールを２
個加えた。まずトリメチルシリルヨージドを３．０グラ
ムを仕込み、液体窒素で冷却して真空引の後に、この中
に２．５グラムのペルフルオロプロペンオキシドを凝縮
させた。次いで反反応管を電気炉で加熱し５日間１５０
℃に保った。反応中は、時折、電気炉より反応管を取り
出して前後、左右に振ってかき混ぜを行った。反応終了
後に、反応ガスを、-78℃、-98℃、-116℃及び-196℃に
冷却したＵ字管を用いて、分別凝縮により分離した。-7
8℃トラップに凝縮した化合物は、薄い黄色い液体(１．
７３グラム)であり、19Ｆ−ＮＭＲやＩＲによる分析の
結果、２−ヨウ化−２，３，３，３−テトラフルオロプ
ロピオン酸フルオリドであることが分かった。その収率
は、仕込んだペルフルオロプロペンオキシド基準で４３
％であった。このものは、更にメチルアルコールと反応
させて、そのメチルエステルとして物性を測定した。分
取ガスクロマトグラフィーにより、精製した２−ヨウ化
−２，３，３，３−テトラフルオロプロピオン酸メチル
エステルは、沸点が71〜72℃、屈折率ｎD 201.4032,密度
ｄ4 201.879の物性値を有する室温では薄いピンク色の液
体である。また、その分光学的データは次のようであ
る。Example 1 As a reaction vessel, a stainless steel reaction tube having a capacity of 100 ml and having a mini-valve made of stainless steel was used. In addition, nickel balls should be placed in the reaction tube for effective stirring.
Added. First, 3.0 g of trimethylsilyl iodide was charged, cooled with liquid nitrogen, evacuated, and then 2.5 g of perfluoropropene oxide was condensed therein. Then, the reaction tube was heated in an electric furnace and kept at 150 for 5 days.
C. During the reaction, the reaction tube was occasionally taken out of the electric furnace and shaken back and forth and left and right to stir. After the completion of the reaction, the reaction gas was separated by fractional condensation using a U-tube cooled to -78 ° C, -98 ° C, -116 ° C and -196 ° C. -7
The compound condensed in the 8 ° C. trap is a pale yellow liquid (1.
As a result of analysis by 19 F-NMR and IR, it was found to be 2-iodine-2,3,3,3-tetrafluoropropionic acid fluoride. The yield is 43 43 based on the perfluoropropene oxide charged.
%Met. This was further reacted with methyl alcohol, and its physical properties were measured as its methyl ester. 2-Iodide-2,3,3,3-tetrafluoropropionic acid methyl ester purified by preparative gas chromatography has a boiling point of 71 to 72 ° C., a refractive index of n D 20 1.4032 and a density of d 4 20 1.879. It is a pale pink liquid at room temperature with physical properties. The spectroscopic data is as follows.
【００１３】ＩＲデータ 2964 (m), 2837 (w), 1763 (vs), 1440 (ms), 1292(s),
1265 (s), 1218(ms), 1184 (ms), 1120 (ms), 1026 (m
s), 889 (ms), 792 (m), 731 (m) , 667(m).ＭＳデータ 286 [M]+ (3.1), 242 CF3CFICH3 + (3.8), 227 CF3CFI+
(11.2), 177CF2I+(8.8), 159 [M-I] + (3.1), 127 I+
(9.8), 100 CF3CF+ (14.2), 69 CF3 + (11.6), 59 C(O)O
CH3 + (100).19 Ｆ-ＮＭＲデータ〔δ(ppm): CFCl3 基準 〕 δ-76.3 ppm (二重線, 3F, -CF3,JF-F=14.1 Hz) δ-140.8 ppm (四重線, 1F, -CF,JF-F=14.1 Hz)[0013]IR data 2964 (m), 2837 (w), 1763 (vs), 1440 (ms), 1292 (s),
1265 (s), 1218 (ms), 1184 (ms), 1120 (ms), 1026 (m
s), 889 (ms), 792 (m), 731 (m), 667 (m).MS data 286 [M]+ (3.1), 242 CFThreeCFICHThree + (3.8), 227 CFThreeCFI+
(11.2), 177CFTwoI+(8.8), 159 [M-I]+ (3.1), 127 I+
(9.8), 100 CFThreeCF+ (14.2), 69 CFThree + (11.6), 59 C (O) O
CHThree + (100).19 F-NMR data [δ (ppm): CFCl 3 standard Δ-76.3 ppm (double line, 3F, -CFThree, JFF= 14.1 Hz) δ-140.8 ppm (Quartet, 1F, -CF, JFF= 14.1 Hz)
───────────────────────────────────────────────────── フロントページの続き 審査官 藤森 知郎 (56)参考文献 特開 昭63−277648（ＪＰ，Ａ) 特開 平２−233640（ＪＰ，Ａ) 特開 平２−262529（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 51/58 C07C 53/50 C07C 67/14 C07C 69/63 ＣＡＰＬＵＳ（ＳＴＮ) ＷＰＩＤＳ（ＳＴＮ)────────────────────────────────────────────────── ─── Continuation of the front page Examiner Toshiro Fujimori (56) References JP-A-63-277648 (JP, A) JP-A-2-233640 (JP, A) JP-A-2-262529 (JP, A) ( 58) Field surveyed (Int.Cl. 7 , DB name) C07C 51/58 C07C 53/50 C07C 67/14 C07C 69/63 CAPLUS (STN) WPIDS (STN)
Claims (2)
ロプロピオン酸フルオリドを製造する方法において、ヘ
キサフルオロプロペンオキシドと、トリメチルシリルヨ
ージドとの反応で合成することを特徴とする２−ヨウ化
−２，３，３，３−テトラフルオロプロピオン酸フルオ
リドの製造方法。1. A method for producing 2-iodine-2,3,3,3-tetrafluoropropionic acid fluoride represented by the following formula (1): CF 3 CFIC (O) F (1) The method for producing 2-iodide-2,3,3,3-tetrafluoropropionic acid fluoride according to the above, wherein the compound is synthesized by reacting hexafluoropropene oxide with trimethylsilyl iodide.
ウ化−２，３，３，３−テトラフルオロプピオン酸エス
テルを製造する方法において、ヘキサフルオロプロペン
オキシドと、トリメチルシリルヨージドとを反応させた
後、得られた２−ヨウ化−２，３，３，３−テトラフル
オロプロピオン酸フルオリドにアルキルアルコールを反
応させることを特徴とする前記方法。2. 2-iodine-2,3,3,3-represented by the following general formula (2): CF 3 CFICOR 1 (2) (wherein R 1 represents an alkyl group) In the method for producing tetrafluoropropionate, hexafluoropropene oxide is reacted with trimethylsilyl iodide, and then the obtained 2-iodine-2,3,3,3-tetrafluoropropionate fluoride is added to The above method, wherein an alkyl alcohol is reacted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11054024A JP3141072B2 (en) | 1999-03-02 | 1999-03-02 | Process for producing 2-iodine-2,3,3,3-tetrafluoropropionic acid fluoride and esters thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11054024A JP3141072B2 (en) | 1999-03-02 | 1999-03-02 | Process for producing 2-iodine-2,3,3,3-tetrafluoropropionic acid fluoride and esters thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000256256A JP2000256256A (en) | 2000-09-19 |
| JP3141072B2 true JP3141072B2 (en) | 2001-03-05 |
Family
ID=12959029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11054024A Expired - Lifetime JP3141072B2 (en) | 1999-03-02 | 1999-03-02 | Process for producing 2-iodine-2,3,3,3-tetrafluoropropionic acid fluoride and esters thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3141072B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195658B (en) * | 2021-12-30 | 2022-12-09 | 湖北孚诺林新材料有限公司 | Method for continuously preparing alkyl penta-fluoropropionate amine ester |
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1999
- 1999-03-02 JP JP11054024A patent/JP3141072B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000256256A (en) | 2000-09-19 |
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