JPH0321485B2 - - Google Patents
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- JPH0321485B2 JPH0321485B2 JP62041160A JP4116087A JPH0321485B2 JP H0321485 B2 JPH0321485 B2 JP H0321485B2 JP 62041160 A JP62041160 A JP 62041160A JP 4116087 A JP4116087 A JP 4116087A JP H0321485 B2 JPH0321485 B2 JP H0321485B2
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- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Fibers (AREA)
- Compounds Of Iron (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規な一般式A1-xTi2+xM5-xO12（ただ
し、ＡはNa、Ｋ、RbまたはCsを、ＭはCa、Al、
FeまたはCrを、ｘは０〜0.5を表わす、以下同
じ）で示される斜方晶系のトンネル構造を有する
繊維状化合物およびその製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is based on a novel general formula A 1-x Ti 2+x M 5-x O 12 (where A represents Na, K, Rb or Cs, M is Ca, Al,
The present invention relates to a fibrous compound having an orthorhombic tunnel structure represented by Fe or Cr (x represents 0 to 0.5, the same applies hereinafter), and a method for producing the same.
該繊維状化合物は陽イオン伝導体、イオン交換
体、触媒、耐熱材、断熱材及び補強材として有用
なものである。 The fibrous compounds are useful as cation conductors, ion exchangers, catalysts, heat-resistant materials, heat insulating materials, and reinforcing materials.
発明の目的
本発明の目的は新規な一般式A1-xTi2+xM5-x
O12で示される斜方晶系トンネル構造を有する繊
維状化合物およびその製造方法を提供するにあ
る。Object of the invention The object of the invention is to provide a novel general formula A 1-x Ti 2+x M 5-x
The present invention provides a fibrous compound having an orthorhombic tunnel structure represented by O 12 and a method for producing the same.
発明の構成
本発明の繊維状化合物は一般式A1-xTi2+xM5-x
O12で示す組成の繊維状物からなり、その構造に
特異性がある。TiはTiO6八面体配位だけである
が、Ｍは四面体配位とMO6八面体配位の２種類
がある。Structure of the Invention The fibrous compound of the present invention has the general formula A 1-x Ti 2+x M 5-x
It consists of a fibrous material with the composition shown by O 12 , and its structure is unique. Ti only has TiO 6 octahedral coordination, but M has two types: tetrahedral coordination and MO 6 octahedral coordination.
トンネル構造の枠組は八面体６個（MO64個と
TiO22個）と四面体２個からなり、MO4−（MO6
−TiO6）−MO6の連鎖の２回対称からなる八角形
を示す。その構造は図面に示す通りで、連鎖で示
したカツコ内は面共有、その他は頂点共有であ
り、Ａイオンはトンネル中に配位する。 The framework of the tunnel structure consists of 6 octahedrons (4 MO 6 and
MO 4 − (MO 6
-TiO 6 )-MO 6 shows an octagon with two-fold symmetry of the chain. Its structure is as shown in the drawing, with the inside of the cutlet shown by the chain being surface-sharing, the others being vertex-sharing, and the A ion is coordinated in the tunnel.
化学量論的組成はA1-xTi2+xM5-xO12式でｘ＝
０の場合である。 The stoichiometric composition is A 1-x Ti 2+x M 5-x O x=
This is the case of 0.
単結晶ではMO6八面体のＭ席を４価のTiでｘ
個置換され、そのために陽イオン電荷調整のた
め、トンネル中のＡ席にｘ個の空席が作られる。
この空席は実施例で示すようにＡ席４個に１個の
割合となり、Ａイオンのイオン伝導に効果的に寄
与するものと考えられる。 In a single crystal, the M seat of the MO 6 octahedron is replaced by tetravalent Ti.
x vacancies are created at the A seat in the tunnel for cation charge adjustment.
As shown in the examples, the number of vacant seats is one in every four A seats, and it is thought that this vacancy contributes effectively to ion conduction of A ions.
この単結晶は固相反応による合成法では粉体は
得られるが、繊維状のものを得ることができなか
つた。本発明は従来未知のA1-xTi2+xM5-xO12で
示される繊維状化合物を得べく研究の結果、下記
の方法によるときは容易に合成し得られることを
究明し得た。 This single crystal could be obtained as a powder by a solid phase reaction synthesis method, but it was not possible to obtain a fibrous single crystal. As a result of research to obtain a previously unknown fibrous compound represented by A 1-x Ti 2+x M 5-x O 12 , the present invention has revealed that it can be easily synthesized by the following method. Ta.
即ち、一般式A2Oあるいは加熱によりA2Oに分
解される化合物と、TiO2あるいは加熱により
TiO2に分解される化合物と、M2O3あるいは加熱
によりM2O3に分解される化合物とを、一般式
（A2O）a（Ti2）b（M2O3）c（ただしａ、ｂ、ｃ＝
0.1〜2.0）で示される組成割合に混合したものあ
るいは固相反応により化合物としたものを結晶原
料とし、一方MoO3あるいは加熱によりMoO3に
分解される化合物とA2Oあるいは加熱によりA2O
に分解される化合物とを、一般式A2O（MoO3）d
（ただし、ｄは0.5〜2.0）で示される組成割合に
混合したものをフラツクス原料とし、結晶原料と
フラツクスとを、モル百分率で50対50〜５対95の
割合に混合した混合物を1200〜1400℃で加熱溶融
し、該溶融体を900〜1000℃まで徐冷することに
よつて得られる。加熱によりA2Oを生成する化合
物としては、例えばAOH、A2CO、AHCO3など
が挙げられる。A2O成分としてはRb2O、Cs2Oは
高価であるので低コストで得るにはNa2O、K2O
であることが好ましい。 That is, a compound with the general formula A 2 O or which decomposes into A 2 O by heating, and TiO 2 or a compound which decomposes into A 2 O by heating.
A compound that decomposes into TiO 2 and a compound that decomposes into M 2 O 3 or M 2 O 3 by heating are expressed by the general formula (A 2 O) a (Ti 2 ) b (M 2 O 3 ) c (where a, b, c=
0.1 to 2.0) or a compound formed by solid phase reaction is used as the crystal raw material, while MoO 3 or a compound that decomposes into MoO 3 by heating and A 2 O or A 2 O by heating are used as crystal raw materials.
A compound that is decomposed into the general formula A 2 O (MoO 3 ) d
(However, d is 0.5 to 2.0. It can be obtained by heating and melting at a temperature of 0.degree. C. and slowly cooling the melt to 900 to 1000.degree. Examples of compounds that generate A 2 O upon heating include AOH, A 2 CO, and AHCO 3 . Since Rb 2 O and Cs 2 O are expensive as A 2 O components, Na 2 O and K 2 O can be obtained at low cost.
It is preferable that
TiO2成分はルチル形でもアナターゼ形であつ
てもよく、また断熱材、補強材などの用途によつ
ては天然物例えばルチルサンド、アナターゼサン
ドであつてもよい。しかし、イオン伝導体材料に
は高純度のものであることが必要である。 The TiO 2 component may be in the rutile form or anatase form, and may also be a natural product such as rutile sand or anatase sand depending on the use as a heat insulating material, reinforcing material, etc. However, the ionic conductor material needs to be of high purity.
M2O3成分は３価の金属酸化物であるGa2O3、
Al2O3、Cr2O3、Fe2O3であり、または加熱により
これらに分解される化合物例えばこれらの水酸化
物などである。その構造で示したように、Ｍ金属
はMO4四面体とMO6八面体の２種類があり、前
者の配位体ではAl2O3、Ga2O3が、後者の配位体
ではGa2O3、Al2O3、Cr2O3、Fe2O3（この場合４
価、５価の金属、例えばTi、Mn、Nb、Ｖなど
と一部置換してもよい。）などが好ましい。 The M 2 O 3 component is Ga 2 O 3 which is a trivalent metal oxide,
Al 2 O 3 , Cr 2 O 3 , Fe 2 O 3 , or compounds that can be decomposed into these by heating, such as their hydroxides. As shown in the structure, there are two types of M metals: MO 4 tetrahedron and MO 6 octahedron . 2 O 3 , Al 2 O 3 , Cr 2 O 3 , Fe 2 O 3 (in this case 4
It may be partially replaced with a valent or pentavalent metal such as Ti, Mn, Nb, V, etc. ) etc. are preferred.
これらの結晶原料の混合割合は一般式（A2O）a
（TiO2）b（M2O3）cで示す。モル比でａ、ｂ、ｃが
0.1〜2.0、好ましくは1.0である。ある成分が0.1
未満であると、目的物は生成しない。また、2.0
を越えてもルチルなどが生成し目的物だけを生成
することはできない。フラツクス原料はMoO3、
A2Oとの割合がA2O（MoO3）dで示される組成割合
とする（ただし、ｄ＝0.5〜2.0を表わす）。ｄが
0.5未満であるとプリデライト、2.0を越えるとル
チルなどが一緒に生成し、目的物だけを生成しな
いので、1.50付近であることが好ましい。 The mixing ratio of these crystal raw materials is expressed by the general formula (A 2 O) a
(TiO 2 ) b (M 2 O 3 ) c . The molar ratio of a, b, and c is
0.1-2.0, preferably 1.0. A certain component is 0.1
If it is less than that, the target product will not be produced. Also, 2.0
Even if the temperature is exceeded, rutile etc. will be produced and it will not be possible to produce only the desired product. The flux raw material is MoO 3 ,
The composition ratio with respect to A 2 O is expressed as A 2 O (MoO 3 ) d (however, d represents 0.5 to 2.0). d is
If it is less than 0.5, pridellite will be produced, and if it exceeds 2.0, rutile will be produced together, and the desired product will not be produced, so it is preferably around 1.50.
結晶原料とフラツクス原料との混合割合はモル
百分率で30〜70であることが好ましい。その割合
が30未満であると、繊維が漸次小さくなり80を越
えると、長繊維になるがコスト高となる。これら
の混合物を1200〜1400℃で加熱する。1200℃未満
では結晶成分の溶解量が少なく、1400℃を越える
と、揮発量が増大し、製造コストも高くなる。 The mixing ratio of the crystal raw material and the flux raw material is preferably 30 to 70 in molar percentage. When the ratio is less than 30, the fibers gradually become smaller, and when it exceeds 80, the fibers become long fibers, but the cost increases. Heat these mixtures at 1200-1400°C. Below 1200°C, the amount of dissolved crystal components is small, and above 1400°C, the amount of volatilization increases and the manufacturing cost increases.
この溶解物を900〜1000℃まで徐冷、例えば５
℃／ｈで徐冷して繊維状に結晶を成長させる。成
長反応は溶解−析出反応であるため徐冷しないと
きは繊維状に成長しないので、徐冷することが必
要である。この徐冷は900〜1000℃まででよく、
後は放冷でよい。 Slowly cool this melt to 900-1000℃, e.g.
It is slowly cooled at ℃/h to grow crystals in the form of fibers. Since the growth reaction is a dissolution-precipitation reaction, it will not grow into a fibrous form unless it is slowly cooled, so slow cooling is necessary. This slow cooling can be done up to 900-1000℃.
After that, you can leave it to cool.
実施例 １
Ko.8Ti2.2Ga4.8O12繊維の合成
K2CO3の特級粉末、TiO299.9％粉末、Ga2O3
99.9％粉末を、（K2O）1.0（TiO2）1.0（Ga2O3）1.0
のモル比割合の結晶原料粉末に、（K2O）1.0
（MoO3）1.25のモル比割合のフラツクス原料粉末
を20対80モル百分率の割合で混合した。この混合
物140ｇを白金ルツボに充填し、炭化けい素発熱
体電気炉を使用して1200℃で溶融させた。溶融時
に炭酸塩が分解して発泡するので、２回に分けて
溶解させた。溶解後1300℃に昇温し約10時間保持
した後、４℃／ｈの速度で1000℃まで徐冷した。
徐冷後炉からルツボを取り出し大気中で室温まで
放冷した。 Example 1 Synthesis of Ko. 8 Ti 2 . 2 Ga 4 . 8 O 12 fiber Special grade K 2 CO 3 powder, TiO 2 99.9% powder, Ga 2 O 3 99.9% powder, (K 2 O) 1.0 (K 2 O) 1.0 is added to the crystal raw material powder with a molar ratio of (TiO 2 ) 1.0 (Ga 2 O 3 ) 1.0 .
(MoO 3 ) Flux raw material powders with a molar ratio of 1.25 were mixed at a ratio of 20:80 molar percentage. 140 g of this mixture was filled into a platinum crucible and melted at 1200° C. using a silicon carbide heating element electric furnace. Since the carbonate decomposes and foams during melting, it was dissolved in two batches. After dissolution, the temperature was raised to 1300°C, held for about 10 hours, and then slowly cooled to 1000°C at a rate of 4°C/h.
After slow cooling, the crucible was taken out of the furnace and allowed to cool to room temperature in the atmosphere.
ルツボを沸とう水に浸漬し、フラツクスを溶解
して結晶を分離し繊維状結晶を得た。繊維状結晶
は0.5〜1.0mmの長さで、直径0.01〜0.1mmの太さの
集合体として生成していた。これを粉末にしてＸ
線回析法で同定したところ目的の結晶であり、そ
の格子定数はａ＝9.256（Å）、ｂ＝16.311（Å）、
ｃ＝2.983（Å）であつた。化学分析して組成を調
べたところ、Ko.8Ti2.2Ga4.8O12であつた。 The crucible was immersed in boiling water to dissolve the flux and separate the crystals to obtain fibrous crystals. The fibrous crystals were formed as aggregates with a length of 0.5 to 1.0 mm and a diameter of 0.01 to 0.1 mm. Make this into powder
The desired crystal was identified by line diffraction, and its lattice constants were a = 9.256 (Å), b = 16.311 (Å),
c=2.983 (Å). Chemical analysis revealed that the composition was Ko. 8 Ti 2 . 2 Ga 4 . 8 O 12 .
K2Oに代えて、Rb2O、Cs2Oを使用し、それぞ
れの金属塩の繊維状化合物が得られた。Na2Oの
場合は不明物質の生成を伴つた。また、Ga2O3に
代えてAl2O3、Cr2O3、Fe2O3を使用し、それぞれ
の相当する組成物が得られた。 By using Rb 2 O and Cs 2 O instead of K 2 O, fibrous compounds of the respective metal salts were obtained. In the case of Na 2 O, an unknown substance was produced. Furthermore, Al 2 O 3 , Cr 2 O 3 , and Fe 2 O 3 were used in place of Ga 2 O 3 and corresponding compositions were obtained.
実施例 ２
Na1.0Ti2.0Al5.0O12繊維の合成
Na2CO3の特級粉末、TiO299.9％粉末、
Al2O399.9％粉末を、（Na2O）1.0（TiO2）1.0
（Al2O3）1.0のモル比割合の結晶原料粉末に、
（Na2O）1.0（MoO3）1.25のモル比割合のフラツクス
原料粉末を、30対70モル百分率割合に混合した。
この混合物140ｇを白金ルツボに充填し、炭化け
い素発熱体電気炉を使用し、1200℃で溶解させ
た。溶解時に炭素塩が分解して発泡するので２回
に分けて溶解させた。溶解後1300℃に昇温し、約
10時間保持した後、４℃／ｈの速度で1000℃まで
徐冷した。徐冷後炉からルツボを取り出し室温ま
で放冷した。Example 2 Synthesis of Na 1 . 0 Ti 2 . 0 Al 5 . 0 O 12 fiber Special grade powder of Na 2 CO 3 , 99.9% TiO 2 powder,
Al 2 O 3 99.9% powder, (Na 2 O ) 1.0 (TiO 2 ) 1.0
(Al 2 O 3 ) Crystal raw material powder with a molar ratio of 1.0 ,
Flux raw material powders having a molar ratio of (Na 2 O) 1.0 (MoO 3 ) 1.25 were mixed at a molar percentage of 30:70.
140 g of this mixture was filled into a platinum crucible and melted at 1200° C. using a silicon carbide heating element electric furnace. Since the carbon salt decomposes and foams during dissolution, it was dissolved in two batches. After melting, the temperature is raised to 1300℃, and approximately
After holding for 10 hours, it was gradually cooled to 1000°C at a rate of 4°C/h. After slow cooling, the crucible was taken out of the furnace and allowed to cool to room temperature.
ルツボを沸とう水に浸漬し、フラツクスを溶解
して結晶を分離した。この結晶は長さ0.5〜1.0
mm、直径0.01〜0.1mmの繊維状結晶の集合体であ
つた。これを粉末にしてＸ線回析法で同定したと
ころ、目的物の結晶であり、その格子定数はａ＝
9.081（Å）、ｂ＝15.520（Å）、ｃ＝2.920（Å）であ
つた。化学分析により組成を調べたところ、
Na0.8Ti2.2Al4.8O12であつた。なお、若干の粒状
結晶が一緒に生成していたがこの物質については
現在のところ同定できていない。 The crucible was immersed in boiling water to dissolve the flux and separate the crystals. This crystal has a length of 0.5~1.0
It was an aggregate of fibrous crystals with a diameter of 0.01 to 0.1 mm. When this was powdered and identified using X-ray diffraction, it was found to be a crystal of the target substance, and its lattice constant was a =
They were 9.081 (Å), b = 15.520 (Å), and c = 2.920 (Å). When we investigated the composition through chemical analysis, we found that
It was Na0.8Ti2.2Al4.8O12 . _ _ _ Note that some granular crystals were also produced, but this substance has not been identified at this time.
Na2Oに代えて、K2O、Rb2O、Cs2Oを使用す
ると、それぞれの金属塩の繊維状化合物が得られ
た。またAl2O3に代えてCr2O3、Fe2O3を使用する
と、Al2O3の八面体配位の席をこれらにより置換
し得られた。 When K 2 O, Rb 2 O, and Cs 2 O were used in place of Na 2 O, fibrous compounds of the respective metal salts were obtained. Furthermore, when Cr 2 O 3 and Fe 2 O 3 were used in place of Al 2 O 3 , the octahedral coordination sites of Al 2 O 3 were replaced by these.
発明の効果
本発明は陽イオン伝導体、イオン交換体、触
媒、耐熱材、断熱材、補強材として有用な新規な
繊維状化合物を提供した優れた効果を有する。Effects of the Invention The present invention has the excellent effect of providing a novel fibrous compound useful as a cation conductor, ion exchanger, catalyst, heat-resistant material, heat insulating material, and reinforcing material.
図面はKTi2Ga5O12結晶の（001）の面上に投
影したトンネル構造を示す。
トンネルの枠組はGaO4−（GaO6−TiO6）−
GaO6連鎖の２回対称からなる八角形を示す。
The drawing shows the tunnel structure projected onto the (001) plane of the KTi 2 Ga 5 O 12 crystal. The framework of the tunnel is GaO 4 − (GaO 6 − TiO 6 ) −
It shows an octagon with two-fold symmetry of GaO 6 chains.
Claims (1)
Ｋ、RbまたはCsを、ＭはGa、Al、FeまたはCr
を、ｘは０〜0.5を表わす）で示される斜方晶系
のトンネル構造を有する繊維状化合物。 ２ 一般式A2O（ただし、ＡはNa、Ｋ、Rbまた
はCsを表わす）または加熱によりA2Oに分解さ
れる化合物と、TiO2または加熱によりTiO2に分
解される化合物と、一般式M2O3（ただし、Ｍは
Ga、Al、FeまたはCrを表わす）または加熱によ
りM2O3に分解される化合物とを、一般式（A2O）
a（TiO2）b（M2O3）c（ただし、ａ、ｂ、ｃはそれ
ぞれ0.1〜2.0を表わす）で示される組成割合に混
合したものあるいはこれらを固相反応させたもの
を結晶原料とし、一方MoO3または加熱により
MoO3に分解される化合物と、一般式A2O（ただ
し、Ａは前記と同じ）または加熱によりA2Oに分
解される化合物とを、一般式A2O（MoO3）d（た
だし、ｄは0.5〜2.0を表わす）で示される組成割
合に混合したものをフラツクス原料とし、結晶原
料とフラツクス原料との混合物を1200〜1400℃で
加熱溶融し、該溶融体を900〜1000℃まで徐冷し
て繊維状単結晶に育成することを特徴とする一般
式A1-xTi2+xM5-xO12で示される斜方晶系のトン
ネル構造を有する繊維状化合物の製造法。[Claims] 1 General formula A 1-x Ti 2+x M 5-x O 12 (A is Na,
K, Rb or Cs, M is Ga, Al, Fe or Cr
, x represents 0 to 0.5), and has an orthorhombic tunnel structure. 2 General formula A 2 O (where A represents Na, K, Rb or Cs) or a compound decomposed to A 2 O by heating, TiO 2 or a compound decomposed to TiO 2 by heating, and general formula M 2 O 3 (However, M is
(representing Ga, Al, Fe or Cr) or a compound that decomposes into M 2 O 3 upon heating, with the general formula (A 2 O)
A mixture of a (TiO 2 ) b (M 2 O 3 ) c (where a, b, and c each represent 0.1 to 2.0) at a composition ratio or a solid phase reaction of these is used as a crystal raw material. and while MoO 3 or by heating
A compound decomposed to MoO 3 and a compound decomposed to A 2 O by the general formula A 2 O (where A is the same as above) or a compound decomposed to A 2 O by heating are expressed by the general formula A 2 O(MoO 3 ) d (however, d represents 0.5 to 2.0) is used as a flux raw material, the mixture of crystal raw material and flux raw material is heated and melted at 1200 to 1400°C, and the melt is slowly heated to 900 to 1000°C. A method for producing a fibrous compound having an orthorhombic tunnel structure represented by the general formula A 1-x Ti 2+x M 5-x O 12 , which comprises growing a fibrous single crystal by cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4116087A JPS63210026A (en) | 1987-02-24 | 1987-02-24 | A fibrous compound having an orthorhombic tunnel structure represented by A↓1↓−↓xTi↓2↓+↓xM↓5↓−↓xO↓1↓2 and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4116087A JPS63210026A (en) | 1987-02-24 | 1987-02-24 | A fibrous compound having an orthorhombic tunnel structure represented by A↓1↓−↓xTi↓2↓+↓xM↓5↓−↓xO↓1↓2 and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63210026A JPS63210026A (en) | 1988-08-31 |
| JPH0321485B2 true JPH0321485B2 (en) | 1991-03-22 |
Family
ID=12600670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4116087A Granted JPS63210026A (en) | 1987-02-24 | 1987-02-24 | A fibrous compound having an orthorhombic tunnel structure represented by A↓1↓−↓xTi↓2↓+↓xM↓5↓−↓xO↓1↓2 and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63210026A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02196027A (en) * | 1989-01-24 | 1990-08-02 | Natl Inst For Res In Inorg Mater | A method for producing fibers or membranes of orthorhombic tunnel structure compound represented by A↓1↓−↓xTi↓2↓+↓xM↓5↓−↓xO↓1↓2 |
| JPH0725544B2 (en) * | 1989-10-23 | 1995-03-22 | 科学技術庁無機材質研究所長 | Heat resistant heat insulating material and manufacturing method thereof |
| EP0776998A4 (en) * | 1995-06-14 | 1998-09-02 | Otsuka Kagaku Kk | TITANATE TRICHITE AND PROCESS FOR PRODUCING THE SAME |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS558449A (en) * | 1978-07-04 | 1980-01-22 | Besesojiyuzunii Nauchinooisusu | Machine for comtinuous metal coating on glass band |
| JPS6011228A (en) * | 1983-06-28 | 1985-01-21 | Natl Inst For Res In Inorg Mater | Heat-resistant heat-insulating material of octotitanate |
| JPS6050727A (en) * | 1983-08-31 | 1985-03-20 | Ricoh Co Ltd | magnetic recording medium |
-
1987
- 1987-02-24 JP JP4116087A patent/JPS63210026A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63210026A (en) | 1988-08-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |