JP3024328B2 - Preparation of amides by hydration of nitriles. - Google Patents
Preparation of amides by hydration of nitriles.Info
- Publication number
- JP3024328B2 JP3024328B2 JP3348379A JP34837991A JP3024328B2 JP 3024328 B2 JP3024328 B2 JP 3024328B2 JP 3348379 A JP3348379 A JP 3348379A JP 34837991 A JP34837991 A JP 34837991A JP 3024328 B2 JP3024328 B2 JP 3024328B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- alcohol
- main
- raney copper
- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はラネー銅触媒の存在下、
メタクリロニトリルと水とを反応させてメタクリルアミ
ドを製造する方法に関する。The present invention relates to the presence of a Raney copper catalyst,
A main polyacrylonitrile and water are reacted to a method of manufacturing the main Takuriruamido.
【０００２】[0002]
【従来の技術】メタクリルアミドは凝集剤、紙力増強
剤、繊維改質剤、ポリマー改質剤、増粘剤、石油回収
剤、土壌改良剤、抄紙用薬剤、ロ水性向上剤等数多くの
用途を有する重合体の原料として極めて重要なモノマー
である。メタクリロニトリルと水とを反応させてメタク
リルアミドを製造するために用いられる触媒としては銅
系触媒が知られており、その中でもラネー銅触媒は代表
的な触媒の一つである。2. Description of the Related Art Methacrylamide is used in many applications, such as flocculants, paper strength agents, fiber modifiers, polymer modifiers, thickeners, oil recovery agents, soil conditioners, papermaking agents, and water improvers. Is a very important monomer as a raw material of a polymer having The catalyst used to produce the main Taku <br/> Riruamido by reacting methacrylonitrile and water are known copper-based catalysts, Raney copper catalysts among which is one of typical catalysts is there.
【０００３】更に、高活性、高選択性への改良方法とし
て、銅に加えてスズ、金、コバルト、ルテニウム等から
なる多元系ラネー触媒が特公昭５２−３３６１２号公報
に開示されており、特開昭５０−８８０２２号公報に
は、銅とアルミニウムの金属合金粒子を展開するとき
に、０より大で２５wt％以下の水酸化アルカリに加え
て、脂肪族ヒドロキシレート化炭化水素化合物等を０よ
り大で２５wt％以下の濃度で添加して処理する方法が開
示されている。Further, as a method for improving high activity and high selectivity, a multi-component Raney catalyst comprising tin, gold, cobalt, ruthenium and the like in addition to copper is disclosed in Japanese Patent Publication No. 52-33612. Japanese Patent Laid-Open Publication No. 50-88022 discloses that when metal alloy particles of copper and aluminum are developed, an aliphatic hydroxylated hydrocarbon compound or the like is added to an alkali hydroxide of greater than 0 and 25 wt% or less. A method of adding and treating at a concentration of at most 25 wt% or less is disclosed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、これら
の方法で得られたラネー銅触媒においても、メタクリロ
ニトリルの水和反応に供した場合、メタクリロニトリル
の転化率及びメタクリルアミドの選択率は必ずしも十分
とは言えず、また、接触水和反応を継続すると触媒経時
的に劣化して活性が低下する。ラネー銅触媒は高価であ
るため、触媒の活性低下を防止し、触媒の寿命を長くす
る方法が望まれている。[SUMMARY OF THE INVENTION However, even in the Raney copper catalyst obtained by these methods, when subjected to the hydration reaction of the main polyacrylonitrile, selection of conversion及beauty main Takuriruamido the main polyacrylonitrile The rate is not always sufficient, and when the catalytic hydration reaction is continued, the catalyst deteriorates with the passage of time and the activity decreases. Since the Raney copper catalyst is expensive, there is a demand for a method of preventing a decrease in the activity of the catalyst and extending the life of the catalyst.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、メタクリ
ロニトリルの水和反応に用いるラネー銅触媒の活性低下
を防止する方法について検討した結果、ラネー銅触媒を
アルコールで洗浄後、メタクリロニトリルの接触水和反
応に用いることにより、ラネー銅触媒の反応活性の低下
を防止できることを見いだし、本発明を完成させた。The present inventors have SUMMARY OF THE INVENTION As a result of studying how to prevent a reduction in activity of the Raney copper catalyst used in the hydration reaction of the main polyacrylonitrile, after washing the Raney copper catalyst in an alcohol, menu The inventors have found that the use of the catalyst for the hydration reaction of acrylonitrile can prevent a decrease in the reaction activity of the Raney copper catalyst, and thus completed the present invention.
【０００６】即ち、本発明は、銅とアルミニウムの合金
をアルカリ水溶液で展開して得られたラネー銅触媒をア
ルコールを用いて洗浄した後に、メタクリロニトリルの
接触水和反応に用いることを特徴とするメタクリルアミ
ドの製造方法である。本発明で用いられるアルコールと
しては、メタノール、エタノール、プロパノール、イソ
プロパノール、フェノール等があげられる。これらの中
で特に好ましいのはメタノールである。Namely, the present invention is a Raney copper catalyst obtained by expanding the copper and aluminum alloys in an alkaline aqueous solution was washed with an alcohol, characterized by using a catalytic hydration reaction of main polyacrylonitrile is a Rume Takuriruamido method of manufacturing to the. Examples of the alcohol used in the present invention include methanol, ethanol, propanol, isopropanol, phenol and the like. Among them, particularly preferred is methanol.
【０００７】又、本発明において用いられるアルコール
は予め溶存する酸素を除去しておくことが好ましい。ラ
ネー銅触媒のアルコールによる洗浄は、回分又は流通方
式で行うことができ、展開して得られたラネー銅触媒に
対して重量当り０．１倍以上、好ましくは１倍以上のア
ルコールを、１〜３００分、好ましくは１０〜１２０分
接触させることが好ましい。アルコールとラネー銅触媒
の接触を良くするために撹はんするとより効果的であ
る。接触させる温度は−２０℃〜１３０℃であるが、好
ましくは１０〜１００℃の範囲である。Further, it is preferable that the alcohol used in the present invention removes dissolved oxygen in advance. Washing of the Raney copper catalyst with an alcohol can be performed in a batch or flow system, and 0.1 to 1 times, preferably 1 or more times the weight of the Raney copper catalyst obtained by developing is preferably 1 to 1 or more. The contact is preferably performed for 300 minutes, preferably 10 to 120 minutes. It is more effective to stir to improve the contact between the alcohol and the Raney copper catalyst. The contacting temperature is from -20C to 130C, preferably from 10C to 100C.
【０００８】アルコール中には水分が含まれていても差
し支えないが、水分の量は９０wt％以下、好ましくは５
０wt％以下、更に好ましくは２０wt％以下である。アル
コールで洗浄した後のラネー銅触媒は水で十分洗浄した
後、メタクリロニトリルの接触水和反応の触媒として供
される。本発明で使用したアルコールは蒸留等の操作に
より精製した後、再使用することもできる。The alcohol may contain water, but the amount of water is preferably 90% by weight or less, preferably 5% by weight or less.
0 wt% or less, more preferably 20 wt% or less. Raney copper catalyst after washing with alcohol washed well with water, it is subjected as a catalyst for catalytic hydration reaction of main polyacrylonitrile. The alcohol used in the present invention can be reused after purification by an operation such as distillation.
【０００９】本発明において、展開して得たラネー銅触
媒をアルコールで洗浄することにより、なぜ触媒の活性
低下が防止できるのかについては明らかではないが、メ
タクリロニトリルの水和反応においてはアルコール処理
したものはメタアクリル酸の副生が少ないことから、ア
ルコール処理により触媒の活性点の変質が防止されるた
めと思われる。In the present invention, it is not clear why washing of the developed Raney copper catalyst with alcohol can prevent a decrease in the activity of the catalyst. However, in the hydration reaction of methacrylonitrile, alcohol treatment is not sufficient. It is presumed that, since the methacrylic acid by-product was little, the treatment with the alcohol prevented deterioration of the active site of the catalyst.
【００１０】一般にラネー銅触媒とは、例えば、「元素
別触媒便覧」４８２〜４９４頁，１９６７年（地人書
館）、「新実験化学講座」第１５巻−II，３９６〜４０
１頁，１９７７年（丸善）等の記載に見られるように、
ニッケル、コバルト、銅又は鉄等の触媒金属３０〜５０
wt％とアルミニウム７０〜５０wt％の合金を、約２０wt
％のアルカリ水溶液によってアルミニウムを溶出（展
開）させることによって得られる金属触媒である。In general, Raney copper catalysts are described in, for example, "Catalyst Handbook by Element", pp. 482-494, 1967 (Jinjinshokan), "New Laboratory Chemistry", Vol. 15-II, 396-40.
As shown in page 1, 1977 (Maruzen), etc.,
Catalyst metal such as nickel, cobalt, copper or iron 30-50
An alloy of 70% to 50% by weight of aluminum and about 50% by weight of aluminum
% Is a metal catalyst obtained by eluting (developing) aluminum with an aqueous alkaline solution of 5%.
【００１１】本発明に用いられるラネー銅触媒は一般
に、銅とアルミニウムの重量％比が３０：７０〜７０：
３０の合金を用いて調製され、展開後に得られる触媒中
の金属の主成分が銅からなる物であるが、銀、金、鉄、
コバルト、ニッケル、ルテニウム、アルミニウム等を１
０wt％以下で含有していても良い。The Raney copper catalyst used in the present invention generally has a weight ratio of copper to aluminum of 30:70 to 70:
The main component of the metal in the catalyst prepared by using the alloy of No. 30 and obtained after development is copper, but silver, gold, iron,
Cobalt, nickel, ruthenium, aluminum, etc.
It may be contained at 0 wt% or less.
【００１２】展開に使用するアルカリの例としては、ナ
トリウム、カリウム、リチウム、セシウム等が挙げられ
るが、ナトリウムを使用することが好ましい。使用する
アルカリ水溶液の濃度は１〜４０wt％、好ましくは１５
〜３５wt％、更に好ましくは２２〜２８wt％の範囲であ
る。アルカリはアルミニウムに対してモル比で１以上、
好ましくは２以上の量を使用するのが良い。Examples of the alkali used for the development include sodium, potassium, lithium, cesium and the like, and it is preferable to use sodium. The concentration of the aqueous alkali solution used is 1 to 40% by weight, preferably 15% by weight.
~ 35 wt%, more preferably 22-28 wt%. The alkali is at least 1 in molar ratio to aluminum,
Preferably, two or more amounts are used.
【００１３】アルカリ水溶液により銅とアルミニウムの
合金を展開する温度は１２０℃以下、好ましくは１００
℃以下が良い。展開時は溶液の温度が一定になるよう
に、該合金の添加と冷却又は加熱を制御する。展開温度
が１２０℃を越えると触媒の活性が低下する。展開に要
する時間は処理する量にもよるが０．１〜１０時間の範
囲が好ましい。展開後は、上澄み液を抜き出した後に十
分な水洗を行ってから反応に供する。The temperature at which the alloy of copper and aluminum is developed with an aqueous alkali solution is 120 ° C. or less, preferably 100 ° C.
C or lower is good. At the time of development, addition of the alloy and cooling or heating are controlled so that the temperature of the solution becomes constant. If the developing temperature exceeds 120 ° C., the activity of the catalyst decreases. The time required for development depends on the amount to be processed, but is preferably in the range of 0.1 to 10 hours. After the development, the supernatant is taken out, washed sufficiently with water, and then subjected to the reaction.
【００１４】本触媒を用いたメタクリロニトリルの水和
反応は少量の触媒によっても進行するが、十分な転化率
を得るためには原料のメタクリロニトリルに対して十分
な量の触媒が必要である。具体的には、懸濁床で反応さ
せる場合、原料のメタクリロニトリル１ｇに対して接触
時間１時間として０．０１〜１００ｇの触媒を用いるこ
とが好ましい。[0014] Hydration of the main polyacrylonitrile using this catalyst proceeds even with a small amount of a catalyst, but a sufficient amount of catalyst relative to the raw material of the main polyacrylonitrile in order to obtain a sufficient conversion rate is necessary. Specifically, when reacted in a suspended bed, it is preferable to use a 0.01~100g catalyst as 1 hour contact time for main polyacrylonitrile 1g of raw material.
【００１５】また、反応温度は３０〜２００℃、好まし
くは５０〜１５０℃の範囲が良い。反応温度が低すぎる
と水和反応の転化率が十分ではなく、又、反応温度が高
すぎると触媒の劣化が大きくなる。本発明のラネー銅触
媒を用いた水和反応は懸濁床又は固定床で行うことがで
きるが、懸濁床で行うことが好ましい。The reaction temperature is in the range of 30 to 200 ° C., preferably 50 to 150 ° C. If the reaction temperature is too low, the conversion of the hydration reaction is not sufficient, and if the reaction temperature is too high, the deterioration of the catalyst becomes large. The hydration reaction using the Raney copper catalyst of the present invention can be performed in a suspension bed or a fixed bed, but is preferably performed in a suspension bed.
【００１６】本発明におけるラネー銅触媒は、使用前及
び使用中において酸素及び酸素を含有するガスとの接触
を避けることが望ましい。本触媒が酸素と接触すると、
反応活性の低下がみられ、また、シアンヒドリン等の副
生成物が増加する。従って、反応器に供給されるラネー
銅触媒、メタクリロニトリル及び水は、これらに溶解し
ている酸素を予め除去しておくことが好ましい。また、
反応器内は酸素を含まない雰囲気に保つことが好まし
い。The Raney copper catalyst in the present invention preferably avoids contact with oxygen and a gas containing oxygen before and during use. When the catalyst comes into contact with oxygen,
The reaction activity is reduced, and by-products such as cyanohydrin increase. Therefore, Raney copper catalyst fed to the reactor, main polyacrylonitrile and water, it is preferable to preliminarily remove oxygen dissolved in these. Also,
It is preferable to keep the inside of the reactor in an atmosphere containing no oxygen.
【００１７】水和反応に供されるメタクリロニトリルと
水との重量比率は実質的に任意であるが、５０：５０〜
５：９５の範囲が好ましい。反応器内は、反応温度と反
応液組成における蒸気圧又はこれに窒素等の不活性ガス
を加えた圧力に保たれるが、その圧力は通常、常圧〜１
０気圧の範囲である。[0017] While the weight ratio of the Rume polyacrylonitrile and water is subjected to a hydration reaction is substantially arbitrarily, 50:50
A range of 5:95 is preferred. In the reactor, the reaction temperature and the vapor pressure at the reaction solution composition or the pressure obtained by adding an inert gas such as nitrogen to the reaction solution are maintained.
The range is 0 atm.
【００１８】水和反応後、反応器から取り出される反応
液は主として未反応のメタクリロニトリルと水と反応生
成物であるメタクリルアミドからなり、更に、シアンヒ
ドリン等の副生成物と銅を含んでいる。この反応液は、
通常、蒸発又は蒸留操作により未反応のメタクリロニト
リルと水の一部を回収すると共に、メタクリルアミドの
濃縮を行う。回収した未反応のメタクリロニトリルと水
は、原料として再利用することができる。[0018] After the hydration reaction, the reaction the reaction solution withdrawn from the instrument consists principally of unreacted main polyacrylonitrile of the water reaction product der Rume Takuriruamido, further comprising by-products and copper such as cyanohydrin In. This reaction solution
Normally, the recovered part of the main polyacrylonitrile and unreacted water by evaporation or distillation, for concentrating the main Takuriruamido. The recovered unreacted main polyacrylonitrile and water can be reused as a raw material.
【００１９】[0019]
【実施例】以下に実施例を挙げて本発明を詳細に説明す
る。 実施例１ ５リットルのフラスコに２４wt％の水酸化ナトリウム水
溶液３０７０ｇを仕込み、約１８０rpm で撹はんしなが
ら窒素ガスでパージし、６０℃に昇温した。次に、日興
リカ（株）社製Ｃｕ−Ａｌ合金粉末（Ｃｕ ５０．１wt
％，Ａｌ ４９．７wt％，Ｆｅ ０．２wt％）２００ｇ
を６０分をかけて添加した。その後、同温度で１時間保
持してから上澄み液を抜き出した。The present invention will be described in detail below with reference to examples. Example 1 A 5-liter flask was charged with 3070 g of a 24 wt% aqueous sodium hydroxide solution, purged with nitrogen gas while stirring at about 180 rpm, and heated to 60 ° C. Next, Nikko Rica Co., Ltd. Cu-Al alloy powder (Cu 50.1 wt.
%, 49.7 wt% Al, 0.2 wt% Fe) 200 g
Was added over 60 minutes. Thereafter, the mixture was kept at the same temperature for 1 hour, and then the supernatant was taken out.
【００２０】次に、このフラスコに予め溶存酸素を除去
しておいたメタノールを３リットル導入して６０℃で３
０分間撹はんした後、上澄み液を抜き出した。次に、予
め溶存酸素を除去しておいた６０℃の温水３リットルを
導入して３０分間撹はんし、上澄み液を抜き出した。こ
の操作を２回繰り返してラネー銅触媒を得た。Next, 3 liters of methanol from which dissolved oxygen had been removed in advance was introduced into the flask,
After stirring for 0 minutes, the supernatant was extracted. Next, 3 liters of warm water at 60 ° C. from which dissolved oxygen had been removed in advance was introduced, and the mixture was stirred for 30 minutes, and the supernatant was extracted. This operation was repeated twice to obtain a Raney copper catalyst.
【００２１】実施例２ 反応器として５００mlのオートクレーブを用い、実施例
１で調製したラネー銅触媒を５０vol.％仕込み、予め溶
存する酸素を除去してあるメタクリロニトリル３０wt
％、水７０wt％の原料を接触時間１時間で反応器に供給
し、１２０℃で反応を行った。反応開始後、１０時間目
のメタクリロニトリルの転化率は７８％、メタクリルア
ミドの選択率は９９．６％であり、８０時間目において
もメタクリロニトリルの転化率は６７％、メタクリルア
ミドの選択率は９９．５％であった。Example 2 A 500 ml autoclave was used as a reactor, 50 vol.% Of the Raney copper catalyst prepared in Example 1 was charged, and 30 wt% of methacrylonitrile from which dissolved oxygen had been removed in advance.
% And 70 wt% of water were supplied to the reactor for a contact time of 1 hour, and the reaction was carried out at 120 ° C. Ten hours after the start of the reaction, the conversion of methacrylonitrile was 78%, the selectivity of methacrylamide was 99.6%, and the conversion of methacrylonitrile was 67%, and the selection of methacrylamide was 80 hours. The rate was 99.5%.
【００２２】比較例１ 実施例１においてメタノール処理をしない以外は同じ操
作を行って得たラネー銅触媒を、実施例２と同様にして
反応を行った。反応開始後、５時間目のメタクリロニト
リルの転化率は７８％、メタクリルアミドの選択率は９
９．３％であったが、１５時間目にはメタクリロニトリ
ルの転化率は６０％、メタクリルアミドの選択率は９
９．０％に低下した。Comparative Example 1 A Raney copper catalyst obtained in the same manner as in Example 1 except that the treatment with methanol was omitted, was reacted in the same manner as in Example 2. Five hours after the start of the reaction, the conversion of methacrylonitrile was 78%, and the selectivity of methacrylamide was 9%.
9.3%, but at 15 hours, the conversion of methacrylonitrile was 60% and the selectivity of methacrylamide was 9
It dropped to 9.0%.
【００２３】実施例３ 実施例１においてメタノールの替わりに水を５０wt％含
んだメタノールで処理する以外は同じ操作を行って得た
ラネー銅触媒を、実施例２と同様にして反応を行った。
反応開始後、１０時間目のメタクリロニトリルの転化率
は７５％、メタクリルアミドの選択率は９９．４％であ
り、５０時間目においてもメタクリロニトリルの転化率
は６０％、メタクリルアミドの選択率は９９．３％であ
った。Example 3 A Raney copper catalyst obtained by performing the same operation as in Example 1 except that methanol containing 50 wt% of water was used instead of methanol to carry out a reaction in the same manner as in Example 2.
Ten hours after the start of the reaction, the conversion of methacrylonitrile was 75%, the selectivity of methacrylamide was 99.4%, and even at 50 hours, the conversion of methacrylonitrile was 60% and the selection of methacrylamide was 50 hours. The rate was 99.3%.
【００２４】[0024]
【発明の効果】アルコール処理したラネー銅触媒をメタ
クリロニトリルと水との接触水和反応に用いることによ
り、ラネー銅触媒の反応活性の低下を防止することがで
き、従って、メタクリルアミドを効率良く製造すること
ができる。 The Raney copper catalyst alcohol treatment according to the present invention by using a catalytic hydration reaction of a meta <br/> acrylonitrile and water, it is possible to prevent a decrease in reaction activity of the Raney copper catalyst, therefore, main Takuriruamido can be efficiently produced.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 231/06 C07C 233/09 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) C07C 231/06 C07C 233/09
Claims (2)
液で展開して得られたラネー銅触媒をアルコールで洗浄
した後に、メタクリロニトリルの接触水和反応の触媒と
して用いることを特徴とするメタクリルアミドの製造方
法。1. A method for producing a Raney copper catalyst, which is obtained by developing an alloy of copper and aluminum with an aqueous alkali solution, washing with an alcohol, and then using the catalyst as a catalyst for a catalytic hydration reaction of methacrylonitrile. Production method.
プロパノール及びイソプロパノールから選ばれる１種以
上のアルコールである請求項１記載のメタクリルアミド
の製造方法。 2. The method according to claim 1, wherein the alcohol is methanol, ethanol,
At least one selected from propanol and isopropanol
The methacrylamide according to claim 1, which is the above alcohol.
Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3348379A JP3024328B2 (en) | 1991-12-05 | 1991-12-05 | Preparation of amides by hydration of nitriles. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3348379A JP3024328B2 (en) | 1991-12-05 | 1991-12-05 | Preparation of amides by hydration of nitriles. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05155831A JPH05155831A (en) | 1993-06-22 |
| JP3024328B2 true JP3024328B2 (en) | 2000-03-21 |
Family
ID=18396632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3348379A Expired - Fee Related JP3024328B2 (en) | 1991-12-05 | 1991-12-05 | Preparation of amides by hydration of nitriles. |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3024328B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095401C (en) * | 1998-05-22 | 2002-12-04 | 中国科学院山西煤炭化学研究所 | Hydrogenolysis catalyst for low-temp synthesis of methanol with methyl formate and its preparing process |
-
1991
- 1991-12-05 JP JP3348379A patent/JP3024328B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05155831A (en) | 1993-06-22 |
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