JPH0560814B2 - - Google Patents
Info
- Publication number
- JPH0560814B2 JPH0560814B2 JP61065125A JP6512586A JPH0560814B2 JP H0560814 B2 JPH0560814 B2 JP H0560814B2 JP 61065125 A JP61065125 A JP 61065125A JP 6512586 A JP6512586 A JP 6512586A JP H0560814 B2 JPH0560814 B2 JP H0560814B2
- Authority
- JP
- Japan
- Prior art keywords
- butylene glycol
- acetaldehyde
- reaction
- aldol
- producing
- 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
Links
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 29
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 14
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 14
- 239000007858 starting material Substances 0.000 claims description 8
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- XOXZKNZCICKTLL-UHFFFAOYSA-N 2,6-dimethyl-1,3-dioxan-4-ol Chemical compound CC1CC(O)OC(C)O1 XOXZKNZCICKTLL-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- FZIIBDOXPQOKBP-UHFFFAOYSA-N 2-methyloxetane Chemical compound CC1CCO1 FZIIBDOXPQOKBP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
〈産業上の利用分野〉
本発明は１，３−ブチレングリコールを製造す
る方法に関するものである。
１，３−ブチレングリコールは各種の合成樹
脂、界面活性剤の原料として、又、化粧品吸湿
剤、高沸点溶剤、不凍液の素材としても有用な物
質である。
〈従来技術及びその問題点〉
従来、１，３−ブチレングリコールの製造方法
としては次の３方法が知られている。
（）アセドアルデヒドをアルドール縮合させ
てアセトアルドールを得、接触還元することによ
つて、１，３−ブチレングリコールを得る（英国
特許第853266号記載）。（）１，３−ブチレンオ
キサイドの加水反応により１，３−ブチレングリ
コールを得る。（）プリンス反応を利用してプ
ロピレンとホルムアルデヒドから１，３−ブチレ
ングリコールを得る。
しかしながら、（）の方法は、工業的製造方
法が未だ確立していないので、実際的で無いこと
は明らかである。又、（）の方法は収率が低い
ので実用的では無い。実際、工業的には（）の
方法で１，３−ブチレングリコールが製造されて
いるが、アセトアルドールは構造的には不安定な
物質であり、脱水してクロトンアルデヒドを生成
したりする為、この方法においては種々の不純
物、例えばブタノール、２−ブタノン等が副生す
る。
殊に、工業的製造における前記アセトアルドー
ルは、それ自身かアセトアルデヒドの三量体であ
るアルドキサン（２，４−ジメチル−１，３−ジ
オキサン−６−オールの慣用名）を主成分として
いることが知られている。（Ind.Eng.Chem.，44，
1003（1952）記載）
このアルドキサンを接触還元すれば、反応機構
上、１，３−ブチレングリコールとエタノールに
水添分解され、前者の製造目的には不都合である
ことは明白である。
〈問題点を解決するための手段〉
本発明者等は１，３−ブチレングリコールを効
率よく製造することを狙い、鋭意努力を重ね、本
発明を完成するに到つた。
即ち、本発明は実質上の有効成分として、パラ
アルドールを含有する出発原料を、接触還元せし
めることを特徴とする１，３−ブチレングリコー
ルの製造方法である。
ところで、アセトアルデヒドの四量体で、且
つ、アセトアルドールの二量体であり、安定な環
状物質であるパラアルドールは接触還元すれば、
反応機構上、目的の１，３−ブチレングリコール
のみしかできない。そして、この事実は机上では
推論できるとしても、今迄これを指摘した文献は
無く、我々が嚆矢とするものである。
出発原料は実質上の有効成分としてパラアルド
ールを含有する混合品又は単品が対象となる。こ
れは、例えば我々が先に出願した「パラアルドー
ルの製造方法」（昭和61年３月13日出願）に従つ
てアセトアルデヒドの縮合反応によるアセトアル
ドールを適切に熱分解することによつて合成され
る。（参考例）
接触還元反応は公知の方法で実施される。通
常、前記出発原料をラネー金属あるいはニツケル
−珪藻土類の水素化用触媒を使用し、圧力50〜80
Kg／cm2、温度100〜120℃で水素添加する。
得られた反応粗液から触媒を分離した後、150
℃以下の温度で減圧蒸溜によつてアルコール等の
低沸分を除去し、さらに続いて精製品（目的物）
を得る。このとき、蒸溜操作において（加熱）温
度及び滞留時間が釜出製品である目的物の品質に
重大な影響を及ぼすことに注意を要する。
〈発明の効果〉
本発明の方法によれば、エタノール等の不純物
の副生を極力抑え、１，３−ブチレングリコール
を効率良く得ることが可能となつた。
〈実施例〉
以下、本発明を参考例、実施例及び比較例によ
り具体的に説明するが、本発明はこれにのみ限定
されるものではない。
なお、各組成分析の測定においては水分はカー
ルフイツシヤー分析器、その他の成分はガスクロ
マトグラフイー、NMR分析器を用いて同定、定
量を行つた。
参考例 （出発原料の調製）
１のジヤケツト付フラスコを利用して、予め
調合したアセトアルデヒド水溶液（アセトアルデ
ヒド／水＝85／15）500gを仕込み、温度15〜20
℃に冷却した。強力に攪拌しながら、10％苛性ソ
ーダ水溶液0.5gを少しずつ滴下し、反応させた。
その間、反応温度20℃に維持した。２時間熟成し
た後、稀酢酸で厳密に中和した（JIS K8006 に
よりフエノールフタレイン指示薬を用いて厳密に
中和した）。得られた生成液の組成はアルドキサ
ン60.0％、アセトアルデヒド25.2％、水14.8％及
び酢酸ナトリウム0.01〜0.02％であつた。
引継いで、連続式フラツシユ蒸発を用いて、上
記生成液を仕込み、加熱調節しながら缶液温度
117℃でアセトアルデヒドを留出させた。滞留時
間は13分、溜出率は44.2％であつた。缶出液の組
成はアルドキサン16.0％、パラアルドール76.2
％、クロトンアルデヒド等2.7％、水5.1％であ
り、溜出液の組成はアセトアルデヒド78.2％、水
21.8％であつた。
実施例 １
１のオートクレーブを利用して、参考例で得
られた缶出液（出発原料）300gを仕込み、ラネ
ー ニツケルを15％添加した後、水素圧力80Kg／
cm2の下で120℃で30分間反応させた。
反応粗液の組成は１，３−ブチレングリコール
85.7％、ブタノール3.4％、エタノール5.3％、水
5.6％であつた。
また、アセトアルデヒド換算に基づく１，３−
ブチレングリコールの選択率は93.0％、エタノー
ルの選択率は5.7％であつた。
実施例２及び比較例
第１表に示した出発原料を変更した以外は、実
施例１と同様に処理した。結果は第１表に示した
通り。
<Industrial Application Field> The present invention relates to a method for producing 1,3-butylene glycol. 1,3-Butylene glycol is a substance useful as a raw material for various synthetic resins and surfactants, and also as a material for cosmetic moisture absorbers, high boiling point solvents, and antifreeze solutions. <Prior art and its problems> Conventionally, the following three methods are known as methods for producing 1,3-butylene glycol. () Acetaldol is obtained by aldol condensation of acetaldehyde, and 1,3-butylene glycol is obtained by catalytic reduction (described in British Patent No. 853266). () 1,3-butylene glycol is obtained by a hydrolysis reaction of 1,3-butylene oxide. () Obtain 1,3-butylene glycol from propylene and formaldehyde using the Prince reaction. However, it is clear that method () is not practical because an industrial manufacturing method has not yet been established. Moreover, the method () has a low yield and is therefore not practical. In fact, 1,3-butylene glycol is industrially produced by the method (), but acetaldol is a structurally unstable substance and can be dehydrated to produce crotonaldehyde. In this method, various impurities such as butanol, 2-butanone, etc. are produced as by-products. In particular, the acetaldol in industrial production is mainly composed of aldoxane (common name for 2,4-dimethyl-1,3-dioxan-6-ol), which is itself a trimer of acetaldehyde. Are known. (Ind.Eng.Chem., 44 ,
1003 (1952)) If this aldoxane is subjected to catalytic reduction, it will be hydrogenolyzed into 1,3-butylene glycol and ethanol due to the reaction mechanism, and it is obvious that this is inconvenient for the purpose of producing the former. <Means for Solving the Problems> The present inventors have made extensive efforts with the aim of efficiently producing 1,3-butylene glycol, and have completed the present invention. That is, the present invention is a method for producing 1,3-butylene glycol, which is characterized by subjecting a starting material containing para-aldol as a substantial active ingredient to catalytic reduction. By the way, para-aldol, which is a tetramer of acetaldehyde and a dimer of acetaldol, and is a stable cyclic substance, is catalytically reduced to produce the following:
Due to the reaction mechanism, only the desired 1,3-butylene glycol can be produced. Although this fact can be inferred on paper, there is no literature that has pointed out this fact until now, and we are the first to do so. The starting materials are mixtures or single products containing para-aldol as a substantial active ingredient. This can be synthesized, for example, by suitably thermally decomposing acetaldol produced by a condensation reaction of acetaldehyde, according to our previously filed "Method for producing para-aldol" (filed on March 13, 1988). . (Reference Example) Catalytic reduction reaction is carried out by a known method. Usually, the starting material is treated with a hydrogenation catalyst of Raney metal or nickel-diatomaceous earth under a pressure of 50 to 80%.
Hydrogenation is carried out at Kg/cm 2 and a temperature of 100-120°C. After separating the catalyst from the obtained reaction crude liquid, 150
Low-boiling components such as alcohol are removed by vacuum distillation at a temperature below ℃, and then the purified product (target product) is purified.
get. At this time, care must be taken that the (heating) temperature and residence time in the distillation operation have a significant effect on the quality of the target product, which is the distilled product. <Effects of the Invention> According to the method of the present invention, it has become possible to efficiently obtain 1,3-butylene glycol while suppressing by-products of impurities such as ethanol as much as possible. <Example> Hereinafter, the present invention will be specifically explained using reference examples, examples, and comparative examples, but the present invention is not limited thereto. In each compositional analysis, water was identified and quantified using a Karl Fischer analyzer, and other components using gas chromatography and NMR analyzers. Reference example (Preparation of starting materials) Using the jacketed flask from 1, charge 500 g of a pre-prepared acetaldehyde aqueous solution (acetaldehyde/water = 85/15) and raise the temperature to 15-20.
Cooled to ℃. While vigorously stirring, 0.5 g of a 10% aqueous solution of caustic soda was added dropwise little by little to cause a reaction.
During this time, the reaction temperature was maintained at 20°C. After aging for 2 hours, it was strictly neutralized with dilute acetic acid (strictly neutralized using a phenolphthalein indicator according to JIS K8006). The composition of the resulting product liquid was 60.0% aldoxane, 25.2% acetaldehyde, 14.8% water, and 0.01-0.02% sodium acetate. Next, using continuous flash evaporation, the above product liquid was charged, and the temperature of the can liquid was adjusted while adjusting the heating.
Acetaldehyde was distilled off at 117°C. The residence time was 13 minutes and the distillation rate was 44.2%. The composition of the bottom liquid is aldoxane 16.0% and para-aldol 76.2%.
%, crotonaldehyde etc. 2.7%, water 5.1%, and the composition of the distillate is acetaldehyde 78.2%, water
It was 21.8%. Example 1 Using the autoclave in 1, charge 300g of the bottom liquor (starting material) obtained in the reference example, add 15% Raney Nickel, and then reduce the hydrogen pressure to 80Kg/
The reaction was carried out for 30 min at 120 °C under cm2 . The composition of the reaction crude liquid is 1,3-butylene glycol
85.7%, butanol 3.4%, ethanol 5.3%, water
It was 5.6%. In addition, 1,3- based on acetaldehyde conversion
The selectivity for butylene glycol was 93.0% and the selectivity for ethanol was 5.7%. Example 2 and Comparative Example The same process as in Example 1 was carried out except that the starting materials shown in Table 1 were changed. The results are shown in Table 1.
【表】【table】
【表】
ここで、実施例等のデータから出発原料中のア
ルドキサンが水添分解され、その略1/3がエタノ
ールに変化している事実が明らかであり、〈従来
技術の問題点〉の項（後半）での仮説を裏づけて
いる。[Table] Here, it is clear from the data such as Examples that the aldoxane in the starting material is hydrogenolyzed and approximately 1/3 of it is converted to ethanol, and the section ``Problems with the Prior Art'' This supports the hypothesis in the second half.
Claims (1)
含有する出発原料を、接触還元せしめることを特
徴とする１，３−ブチレングリコールの製造方
法。1. A method for producing 1,3-butylene glycol, which comprises subjecting a starting material containing para-aldol as a substantial active ingredient to catalytic reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61065125A JPS62246529A (en) | 1986-03-24 | 1986-03-24 | Production of 1,3-butylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61065125A JPS62246529A (en) | 1986-03-24 | 1986-03-24 | Production of 1,3-butylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62246529A JPS62246529A (en) | 1987-10-27 |
| JPH0560814B2 true JPH0560814B2 (en) | 1993-09-03 |
Family
ID=13277838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61065125A Granted JPS62246529A (en) | 1986-03-24 | 1986-03-24 | Production of 1,3-butylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62246529A (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3285439B2 (en) * | 1993-03-24 | 2002-05-27 | ダイセル化学工業株式会社 | Method for producing reaction crude liquid and method for producing 1,3-butylene glycol |
| EP0787709B1 (en) * | 1993-03-24 | 2000-03-08 | Daicel Chemical Industries, Ltd. | An improved process for the preparation of 1,3-betylene glycol |
| JP3369707B2 (en) * | 1994-03-17 | 2003-01-20 | ダイセル化学工業株式会社 | Purification method of 1,3-butylene glycol |
| KR20010102420A (en) | 2000-02-04 | 2001-11-15 | 고지마 아끼로, 오가와 다이스께 | High-purity 1,3-butylene glycol, process for producing 1,3-butylene glycol, and process for producing by-product butanol and butyl acetate |
| JP4530461B2 (en) * | 2000-02-04 | 2010-08-25 | ダイセル化学工業株式会社 | Method for purifying 1,3-butylene glycol |
| CN105585448B (en) * | 2016-03-09 | 2019-11-05 | 辽宁科隆精细化工股份有限公司 | A method of synthesis cosmetics-stage 1,3 butylene glycol |
| CN108383684B (en) * | 2018-03-28 | 2021-07-30 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of synthetic method and system of 1,3-butanediol |
| JP6804601B1 (en) * | 2019-09-05 | 2020-12-23 | 株式会社ダイセル | 1,3-butylene glycol products |
| JP6890709B2 (en) * | 2019-09-05 | 2021-06-18 | 株式会社ダイセル | 1,3-butylene glycol products |
| JP6979473B2 (en) * | 2020-01-07 | 2021-12-15 | 株式会社ダイセル | 1,3-butylene glycol products |
| JP6890708B2 (en) * | 2019-09-05 | 2021-06-18 | 株式会社ダイセル | 1,3-butylene glycol products |
| JP6804602B1 (en) * | 2019-09-05 | 2020-12-23 | 株式会社ダイセル | 1,3-butylene glycol products |
| EP4026825A4 (en) * | 2019-09-05 | 2023-11-29 | Daicel Corporation | 1,3-BUTYLENE GLYCOL PRODUCT |
| JP7380161B2 (en) * | 2019-12-09 | 2023-11-15 | 株式会社レゾナック | Method for producing paraaldol |
| JP7380181B2 (en) * | 2019-12-20 | 2023-11-15 | 株式会社レゾナック | Method for producing paraaldol |
-
1986
- 1986-03-24 JP JP61065125A patent/JPS62246529A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62246529A (en) | 1987-10-27 |
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