JPS6350341B2 - - Google Patents
Info
- Publication number
- JPS6350341B2 JPS6350341B2 JP11870184A JP11870184A JPS6350341B2 JP S6350341 B2 JPS6350341 B2 JP S6350341B2 JP 11870184 A JP11870184 A JP 11870184A JP 11870184 A JP11870184 A JP 11870184A JP S6350341 B2 JPS6350341 B2 JP S6350341B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylmethylacrylamide
- temperature
- water
- formula
- solution
- 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
Links
- -1 vinyl compound Chemical class 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
- CCIDRBFZPRURMU-UHFFFAOYSA-N 2-methyl-n-propylprop-2-enamide Chemical compound CCCNC(=O)C(C)=C CCIDRBFZPRURMU-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GEHLEADVHVVTET-UHFFFAOYSA-N ethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[NH2+]C GEHLEADVHVVTET-UHFFFAOYSA-N 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、側鎖にＮ，Ｎ−エチルメチルアクリ
ルアミド基をもつビニル化合物に関する。
本発明者らは、先に、Ｎ−イソプロピルアクリ
ルアミド、Ｎ−イソプロピルメタクリルアミド、
Ｎ−ｎ−プロピルアクリルアミド又はＮ−ｎ−プ
ロピルメタクリルアミドの重合体は、転移温度以
下の低温域では親水性でその水溶液は透明であ
り、加熱し転移温度より高くなると疎水性に変わ
り、不透明化する性質を有することを見出し、こ
の性質を利用して遮光材料とすることを提案し
た。
しかしながら、上記の重合体は、いずれもその
水溶液の転移温度が45℃以下であり、その利用範
囲がかなり限定される。
本発明者らは、更に異つた転移温度をもち、よ
り利用範囲の拡大された材料を開発すべく研究を
続けた結果、文献未載の新規なビニル化合物
（）を合成し、更にその重合体
The present invention relates to a vinyl compound having an N,N-ethylmethylacrylamide group in its side chain. The present inventors previously discovered N-isopropylacrylamide, N-isopropylmethacrylamide,
The polymer of N-n-propylacrylamide or N-n-propylmethacrylamide is hydrophilic and its aqueous solution is transparent at low temperatures below the transition temperature, but when heated to a temperature higher than the transition temperature, it becomes hydrophobic and becomes opaque. We discovered that this property has the property of shading and proposed to make use of this property as a light-shielding material. However, the above-mentioned polymers all have a transition temperature of 45° C. or less in their aqueous solutions, which limits their range of use considerably. The present inventors continued their research to develop materials with different transition temperatures and a wider range of applications, and as a result, synthesized a new vinyl compound () that has not been described in the literature, and
【式】は、可逆的に低温で水に溶
け、高温では不溶となる性質を有すること、すな
わち溶液状態でラジカル重合させた１重量％ポリ
（Ｎ，Ｎ−エチルメチルアクリルアミド）水溶液
の転移温度は、重合条件にもよるが、54〜57℃の
間の転移温度を有することを見出し、本発明をな
すに至つた。
本発明のビニル化合物は、文献未載の新規化合
物であり、例えば、次のように合成される。
ここで用いられる溶媒は、CH2＝CH−COClと
反応しない溶媒に限定され、アルコール類、アミ
ン類は不可であるが、それ以外の溶媒については
特に制限はなく、一般にはベンゼン、アセトン、
トルエン等が用いられる。反応温度は溶媒の種類
その他の条件により異なるが10℃未満が望まし
い。10℃以上では、副反応がおこりビニル化合物
の生成が困難になる。
このようにして得られる反応混合物から、目的
化合物を単離するには、まずろ過によりトリエチ
ルアミン塩酸塩、あるいはＮ，Ｎ−エチルメチル
アミン塩酸塩を除去し、更にろ液からロータリー
エバポレーターを用いて溶媒を除去し、次いで減
圧蒸留する。減圧蒸留の際、不純物が混入して着
色している場合は、再蒸留により精製して、高純
度のものとすることができる。目的物Ｎ，Ｎ−エ
チルメチルアクリルアミド（65℃／１mmHg）は
無色透明な液体である。
本発明のビニル化合物の溶解特性については、
水、メチルアルコール、エチルアルコール、Ｎ，
Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホ
ルムアミド、ジメチルスルホキシド、アセトン、
ジオキサン、テトラヒドロフラン、クロロホル
ム、四塩化炭素等に可溶であり、ｎ−ヘキサン、
ｎ−ヘプタンには相分離する。
本発明のビニル化合物は、[Formula] has the property of being reversibly soluble in water at low temperatures and insoluble at high temperatures, that is, the transition temperature of a 1% by weight aqueous solution of poly(N,N-ethylmethylacrylamide) radically polymerized in a solution state is The present inventors have discovered that the polymer has a transition temperature of 54 to 57°C, depending on the polymerization conditions, and have accomplished the present invention. The vinyl compound of the present invention is a novel compound that has not been described in any literature, and is synthesized, for example, as follows. The solvent used here is limited to those that do not react with CH 2 = CH-COCl, and alcohols and amines are not allowed, but there are no particular restrictions on other solvents, and generally benzene, acetone,
Toluene etc. are used. The reaction temperature varies depending on the type of solvent and other conditions, but is preferably less than 10°C. At temperatures above 10°C, side reactions occur and it becomes difficult to produce vinyl compounds. To isolate the target compound from the reaction mixture thus obtained, firstly, triethylamine hydrochloride or N,N-ethylmethylamine hydrochloride is removed by filtration, and then the filtrate is purified using a rotary evaporator to remove the solvent. is removed and then distilled under reduced pressure. If the product is colored due to impurities mixed in during vacuum distillation, it can be purified by redistillation to make it highly pure. The target product, N,N-ethylmethylacrylamide (65°C/1 mmHg), is a colorless and transparent liquid. Regarding the solubility characteristics of the vinyl compound of the present invention,
water, methyl alcohol, ethyl alcohol, N,
N-dimethylformamide, N,N-diethylformamide, dimethyl sulfoxide, acetone,
It is soluble in dioxane, tetrahydrofuran, chloroform, carbon tetrachloride, etc., and is soluble in n-hexane,
Phase separation occurs in n-heptane. The vinyl compound of the present invention is
【式】−CO−Ｎ、
CH2＝CH−
の各基を有するので、IRスペクトル、NMRスペ
クトル、マススペクトルによつて同定することが
できる。
本発明のビニル化合物の重合体は、低温域で水
に溶け、高温域で水に不溶となる高温疎水化型の
熱可逆高分子である。このポリマーは水中に於け
る熱可逆特性を利用し、吸着剤、遮光体等多方面
に利用できる。
次に実施例および参考例によつて、本発明をさ
らに詳細に説明する。
実施例 １
１の三角フラスコにトリエチルアミン38.5
ml、エチルメチルアミン25ml及びベンゼン450ml
を入れ、氷で冷やして、内溶液を10℃未満の温度
に保ち、かきまぜながら、この中にアクリル酸ク
ロリド23mlとベンゼン50mlの混合溶液を滴下漏斗
から約３時間かけてゆつくりと滴下した。滴下完
了後、反応液を１昼夜放置冷却したのち、ろ過
し、ロータリーエバポレータを用いて、ろ液から
ベンゼンを除去し濃縮した。次いで減圧蒸留して
沸点65℃／１mmHg、無色透明の留分を回収した。
以上の操作より液状物質22.6ｇを得た。
この物質のマススペクトルを第１図に、赤外線
吸収スペクトルを第２図に、NMRスペクトルを
第３図に示す。
これらスペクトルの分析の結果は、次のとおり
である。
質量分析：
ｍ／ｅ＝113[Formula] Since it has each group of -CO-N and CH 2 =CH-, it can be identified by IR spectrum, NMR spectrum, and mass spectrum. The vinyl compound polymer of the present invention is a high-temperature hydrophobized thermoreversible polymer that dissolves in water at low temperatures and becomes insoluble in water at high temperatures. This polymer takes advantage of its thermoreversible properties in water and can be used in many ways, including as an adsorbent and a light shield. Next, the present invention will be explained in more detail with reference to Examples and Reference Examples. Example 1 Triethylamine 38.5% in 1 Erlenmeyer flask
ml, ethylmethylamine 25ml and benzene 450ml
was added, cooled with ice, and kept at a temperature below 10°C. While stirring, a mixed solution of 23 ml of acrylic acid chloride and 50 ml of benzene was slowly dropped into the solution from a dropping funnel over a period of about 3 hours. After completion of the dropwise addition, the reaction solution was left to cool for a day and night, filtered, and concentrated using a rotary evaporator to remove benzene from the filtrate. Then, it was distilled under reduced pressure to recover a colorless and transparent fraction with a boiling point of 65° C./1 mmHg.
Through the above operations, 22.6 g of a liquid substance was obtained. The mass spectrum of this substance is shown in Figure 1, the infrared absorption spectrum in Figure 2, and the NMR spectrum in Figure 3. The results of analysis of these spectra are as follows. Mass spectrometry: m/e=113
【式】 （親ピーク） ｍ／ｅ＝27 CH2＝CH− （フラグメントピーク） ｍ／ｅ＝55 CH2＝CH−CO− （フラグメントピーク） ｍ／ｅ＝58[Formula] (Parent peak) m/e=27 CH 2 =CH- (Fragment peak) m/e=55 CH 2 =CH-CO- (Fragment peak) m/e=58
【式】 （フラグメントピーク） ｍ／ｅ＝98 CH2＝CH−CO−NH−CH2CH3 （フラグメントピーク） IR分析：3500CM-1（−Ｎ＜） 1648CM-1（＞Ｃ＝Ｏ） 1608CM-1（CH2＝CH−） 980CM-1（CH2＝CH−） NMR分析：0.96ppm（−CH2−CH3のCH3） 1.15ppm（−CH3） 1.50ppm（−CH2−） 5.60ppm（[Formula] (Fragment peak) m/e=98 CH 2 = CH-CO-NH-CH 2 CH 3 (Fragment peak) IR analysis: 3500CM -1 (-N<) 1648CM -1 (>C=O) 1608CM -1 (CH 2 = CH-) 980CM -1 (CH 2 = CH-) NMR analysis: 0.96ppm (-CH 2 -CH 3 of CH 3 ) 1.15ppm (-CH 3 ) 1.50ppm (-CH 2 -) 5.60ppm (
【式】のHa） 6.12ppm（[Formula] Ha) 6.12ppm (
【式】のHb） 6.25ppm（[Formula] Hb) 6.25ppm (
【式】のHc）
以上の分析結果から、この物質はＮ，Ｎ−エチ
ルメチルアクリルアミドであることが確認され
た。
参考例
実施例で得たＮ，Ｎ−エチルメチルアクリルア
ミド4.69ｇ及び１％アゾビスイソブチロニトリル
を含むメタノール溶液17.45ｇをアンプルに入れ、
液体窒素を用いて減圧脱気を行い、上部をバーナ
で封じた。このアンプルを50℃の恒温槽に２時間
浸漬して重合反応を行わせた。重合反応後、アン
プルに少量のハイドロキノンを加え反応を停止さ
せ、ロータリーエバポレータを用いてメタノール
を除去したのち、アセトン溶液とし、さらにジエ
チルエーテル中に投入して未反応モノマーを溶解
させ、不溶部分を回収した（収量3.47ｇ）。得ら
れたポリマーをクロロホルム溶液とし、ウベロー
デ粘度計を用いて粘度測定した結果、その極限粘
度〔η〕は0.62であつた。
得られたポリ（Ｎ，Ｎ−エチルメチルアクリル
アミド）を水に溶解して、１重量％水溶液を調整
し、この水溶液を昇温速度１℃／minで昇温させ
ながら分光光度計を用いて、500nｍの透過率と
温度との関係を求めた。この結果をグラフとして
第４図に示す。
このグラフから明らかなように、ポリ（Ｎ，Ｎ
−エチルメチルアクリルアミド）は、低温域では
水に溶解しているが、54℃より析出しはじめ55℃
では500nｍの透過率が０％となり、水に不溶と
なることがわかる。Hc of [Formula]) From the above analysis results, it was confirmed that this substance was N,N-ethylmethylacrylamide. Reference Example Put 4.69 g of N,N-ethylmethylacrylamide obtained in Example and 17.45 g of a methanol solution containing 1% azobisisobutyronitrile into an ampoule,
Degassed under reduced pressure using liquid nitrogen, and the upper part was sealed with a burner. This ampoule was immersed in a constant temperature bath at 50° C. for 2 hours to carry out a polymerization reaction. After the polymerization reaction, add a small amount of hydroquinone to the ampoule to stop the reaction, remove methanol using a rotary evaporator, make an acetone solution, and then pour it into diethyl ether to dissolve unreacted monomers and recover the insoluble portion. (yield 3.47g). The obtained polymer was made into a chloroform solution, and the viscosity was measured using an Ubbelohde viscometer, and the intrinsic viscosity [η] was 0.62. The obtained poly(N,N-ethylmethylacrylamide) was dissolved in water to prepare a 1% by weight aqueous solution, and while raising the temperature of this aqueous solution at a temperature increase rate of 1°C/min, using a spectrophotometer, The relationship between transmittance at 500 nm and temperature was determined. The results are shown in FIG. 4 as a graph. As is clear from this graph, poly(N, N
- Ethylmethylacrylamide) is dissolved in water at low temperatures, but begins to precipitate at 54°C and 55°C.
It can be seen that the transmittance at 500 nm is 0%, indicating that it is insoluble in water.
第１図は、Ｎ，Ｎ−エチルメチルアクリルアミ
ドのマススペクトル、第２図は、Ｎ，Ｎ−エチル
メチルアクリルアミドの赤外線吸収スペクトル、
第３図は、Ｎ，Ｎ−エチルメチルアクリルアミド
のNMRスペクトルを示す。第４図は、ポリ
（Ｎ，Ｎ−エチルメチルアクリルアミド）１重量
％水溶液についての温度と500nｍでの透過率と
の関係を示す。
Figure 1 shows the mass spectrum of N,N-ethylmethylacrylamide, Figure 2 shows the infrared absorption spectrum of N,N-ethylmethylacrylamide,
FIG. 3 shows the NMR spectrum of N,N-ethylmethylacrylamide. FIG. 4 shows the relationship between temperature and transmittance at 500 nm for a 1% by weight aqueous solution of poly(N,N-ethylmethylacrylamide).
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11870184A JPS6151A (en) | 1984-06-08 | 1984-06-08 | Novel vinyl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11870184A JPS6151A (en) | 1984-06-08 | 1984-06-08 | Novel vinyl compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6151A JPS6151A (en) | 1986-01-06 |
| JPS6350341B2 true JPS6350341B2 (en) | 1988-10-07 |
Family
ID=14743000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11870184A Granted JPS6151A (en) | 1984-06-08 | 1984-06-08 | Novel vinyl compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6151A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL89371A (en) * | 1988-02-24 | 1993-07-08 | Us Commerce | Polyacrylamide gels, their preparation and their use for detection and separation of proteins |
-
1984
- 1984-06-08 JP JP11870184A patent/JPS6151A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6151A (en) | 1986-01-06 |
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