JPS6352054B2 - - Google Patents
Info
- Publication number
- JPS6352054B2 JPS6352054B2 JP59142582A JP14258284A JPS6352054B2 JP S6352054 B2 JPS6352054 B2 JP S6352054B2 JP 59142582 A JP59142582 A JP 59142582A JP 14258284 A JP14258284 A JP 14258284A JP S6352054 B2 JPS6352054 B2 JP S6352054B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- methyl methacrylate
- acetone
- acrylonitrile
- copolymer
- 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
- 229920001577 copolymer Polymers 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 27
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 25
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 239000011342 resin composition Substances 0.000 claims description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 6
- 229920003244 diene elastomer Polymers 0.000 claims description 6
- 229920002857 polybutadiene Polymers 0.000 claims description 6
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical group CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims 1
- 239000011115 styrene butadiene Substances 0.000 claims 1
- 229920003048 styrene butadiene rubber Polymers 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 239000002245 particle Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 229920000578 graft copolymer Polymers 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 229920001893 acrylonitrile styrene Polymers 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920012128 methyl methacrylate acrylonitrile butadiene styrene Polymers 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920006352 transparent thermoplastic Polymers 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は高度の透明性と衝撃強さを有し、しか
も良好な耐熱性を有する熱可塑性樹脂組成物に関
するものである。
〔従来の技術〕
アクリロニトリル−スチレン共重合体はかたく
透明で耐薬品性に優れ、又経済性にも優れた熱可
塑性樹脂であるが、衝撃強さが低いと言う欠点が
あり、用途により優れた衝撃強さを要求されるこ
とが多い。その為例えばゴムにアクリロニトリル
とスチレンをグラフト重合することによつて衝撃
強さを改良することが行なわれている。このよう
な樹脂はABS樹脂として知られ今日広く使われ
ているが、通常アクリロニトリル−スチレン共重
合体の特徴である透明性が損なわれ不透明であ
る。分散ゴムの粒子径を可視光の波長より十分小
さくすれば透明性は向上するが同時に衝撃強さは
著しく低下してしまう。ABS樹脂が本来有して
いる特性を損なうことなく透明性を付与する為に
は、分散粒子の屈折率と連続相の屈折率を一致さ
せることが必要で、エンサイクロペデイア・オ
ブ・ポリマー・サイエンス・アンド・テクノロジ
ー、サプレメント（Encyclopedia of Polymer
Science and Technology、Supplement）第１
巻、第307〜318頁、インターサイエンス、ニユー
ヨーク（Interscience、New York）（1976）に
詳細な記述があるとおりメチルメタクリレートを
加えた、例えばゴムにアクリロニトリル、スチレ
ン、メタクリレートをグラフト重合させて得られ
る、いわゆるMABS樹脂が公知である。この
MABS樹脂は確かに良好な透明性と衝撃強さを
有しているが、反面トランスアクシヨンズ・オ
ブ・ザ・フアラデイ・ソサイエテイ
（Transactions of the Faraday Society）、No.
56、1529〜1534（1960）に記されているようにア
クリロニトリル−メチルメタクリレートの結合を
多くすれば耐熱性が著しく低下してしまう。その
為特公昭44−15902号公報ではスチレンをα−メ
チルスチレンにかえアクリロニトリル−α−メチ
ルスチレン−メチルメタクリレート共重合体とグ
ラフト共重合体をブレンドすることによつて耐熱
性が高く透明性の良い樹脂組成物を得る方法が紹
介されているものの、得られた樹脂の加工流動性
が低く大型、或いは形状の複雑な成形品では黄変
しやすいばかりか満足すべき透明性も得難く、そ
の商品価値は低い。一方特公昭39−8667号公報で
はポリメチルメタクリレートとグラフト共重合体
をブレンドしているが、グラフト共重合体に使用
されるゴムラテツクスの粒子径は0.1ミクロン以
下という極めて小さいものが優位量であるので衝
撃強さは不十分で、又耐熱性の低いグラフト共重
合体を多くブレンドしているので、得られた組成
物の透明性及び耐熱性はやはり低いものとなつて
いる。更に特公昭55−7882号公報は共重合成分と
してアルキルアクリレートを10重量％以下含んだ
メチルメタクリレート重合物（成分Ａ）と共重合
成分としてアクリロニトリルを12〜22重量％含ん
だアクリロニトリル−スチレン重合物（成分Ｂ）
と−30℃以下のガラス転移点を有するゴムにアク
リロニトリル及びスチレンをグラフト重合して得
たグラフト共重合物（成分Ｃ）をブレンドし成分
Ｃの屈折率と成分Ａ及びＢの屈折率とを一致させ
ることによつて透明な成形材料を得るものである
が、メチルメタクリレート系樹脂と相溶するアク
リロニトリル−スチレン共重合体としてはアクリ
ロニトリル含有量が15重量％付近のものを選ばな
ければならない為、得られる成形材料の耐薬品性
は、いわゆるABS樹脂に比べて劣り、又実施例
（試験１〜４）に見られるように成形材料の耐衝
撃性を高める為に耐熱性の低い成分Ｃを多くブレ
ンドしているので、成形材料の耐熱性も低いと考
えられる。
〔本発明が解決しようとする問題点〕
本発明者らはABS樹脂が本来有している優れ
た耐衝撃性を損なうことなく高度に透明な熱可塑
性樹脂組成物を得る目的でABS樹脂とメチルメ
タクリレート共重合体との２成分系組成物につい
て詳細な検討を加えた。
〔問題点を解決するための手段〕
その結果、メチルメタクリレートとアクリロニ
トリルの共重合体が一般に使用されているABS
樹脂と相溶性を有すること、しかも得られる組成
物の衝撃強さは同量のゴム含有量のABS樹脂に
比べて飛躍的に向上することを見い出した。この
事実は本発明の目的に対して重要な意味をもつも
のであつて、ある一定の衝撃強さを有する透明な
熱可塑性樹脂を得るのに従来の方法に比べガラス
転移温度が低いゴム粒子の量を少なくできるの
で、より一層透明性を高めることが可能になると
同時に耐熱性も向上させることができるのであ
る。
すなわち本発明は、アクリロニトリル22〜35重
量％、スチレン45〜78重量％、α−メチルスチレ
ン０〜20重量％の共重合体とポリブタジエン、或
いはブタジエンを85重量％以上含有するジエン系
ゴムからなり、グラフト率が10〜40重量％である
ABS樹脂とメチルメタクリレート70〜99重量％
及びアクリロニトリル１〜20重量％、その他の共
重合可能な単量体０〜10重量％からなるメチルメ
タクリレート共重合体とから基本的になる組成物
において、(A)組成物中のアセトン不溶分量が５〜
30重量％で、しかもアセトン不溶分の10重量％メ
チルエチルケトン溶液粘度が３〜10センチポイズ
であり、(B)アセトン不溶分の屈折率（n25 D）をａ、
アセトン可溶分の屈折率をｂとすれば、
｜ａ−ｂ｜≦0.005
の範囲であることを特徴とする熱可塑性樹脂組成
物に関するものである。
〔発明の効果〕
本発明の特徴を有する組成物は２成分間の相溶
性が極めて高く成形加工温度に対する透明性の依
存性が認められないので、たとえ大型、或いは複
雑な形状を有する成形品でも容易に得ることが可
能である。例えば特開昭57−126812号公報に見ら
れるように、グラフト重合体のグラフト率を十分
高くしなければ透明性、衝撃強さに優れた樹脂組
成物は得難いというのがこれまでの一般的な考え
方であつた。しかしながら本発明ではABS樹脂
のグラフト率が10〜40重量％の範囲において透明
性と衝撃強さという相反する特性を同時に高める
ことができ、しかも耐熱性も向上できたという事
実は過去の文献や特許公報から全く予測できず本
発明によつて初めて明らかにされた事実である。
〔作用〕
本発明の熱可塑性樹脂組成物を構成するABS
樹脂及びメチルメタクリレート共重合体はそれぞ
れ前記成分組成からなる重合体であることが必要
である。ABS樹脂における共重合体中のアクリ
ロニトリル量が22重量％より少ないと耐薬品性等
の特性が低下し、又35重量％を超えると得られる
組成物の熱変色が大きくなるので好ましくない。
アクリロニトリル量が25〜33重量％の範囲では特
に透明性、衝撃強さに優れた組成物が得られる。
共重合体中のスチレンの一部をα−メチルスチレ
ンに置き換えることによつて更に耐熱性を高める
ことも可能であるが、α−メチルスチレン量が20
重量％を超えると加工流動性が低下し成形品が黄
変しやすくなるばかりでなく透明性、衝撃強さと
もに低下するので本発明の目的が達成できなくな
つてしまう。又、ジエン系ゴムのブタジエン量が
85重量％より少ないと衝撃強さが低下する。15重
量％以下の他の単量体としては、例えば、スチレ
ン、アクリロニトリル等を挙げることができる。
ABS樹脂のグラフト率が10重量％より小さいと
衝撃強さが低下し、逆に40重量％より大きいと透
明性が低下する。グラフト率が40重量％より大き
いと透明性が低下する理由の詳細は不明である
が、本発明に関する実験結果によれば、グラフト
したアクリロニトリル−スチレン−α−メチルス
チレン共重合体は分散ゴム粒子の屈折率に影響を
及ぼすので、グラフト率が高いと分散ゴム粒子が
実質的に屈折率の異なる２層で構成されるように
なる為と推測される。グラフト率が20〜35重量％
の範囲では分散ゴム粒子が組成物中に均一に相溶
した状態にあるので特に高い透明性と衝撃強さを
有する組成物が得られる。
ABS樹脂のグラフト率とは、室温でアセトン
に対する可溶分を抽出し残つたアセトン不溶分の
乾燥重量（ｕ）を測定し、この重量とABS樹脂
の製造に使用されたポリブタジエン、或いはジエ
ン系ゴムの重量（ｖ）との差をグラフトした単量
体の重量として次式により算出した。
グラフト率＝ｕ−ｖ／ｖ×100（％）
メチルメタクリレート共重合体は共重合成分で
あるアクリロニトリルが20重量％を超えると
ABS樹脂に対する相溶性が悪化し、組成物の透
明性、衝撃強さともに低下してしまう。アクリロ
ニトリルが５〜15重量％の範囲でABS樹脂に対
する相溶性が非常に高くなり、優れた透明性と衝
撃強さが得られる。又、メチルメタクリレート及
びアクリロニトリルと共重合可能な単量体として
はスチレン、メチルアクリレート、メタクリロニ
トリルを挙げることができる。
ABS樹脂とメチルメタクリレート共重合体か
らなる組成物中のアセトン不溶分量は５〜30重量
％で、５重量％より少ないと衝撃強さが低くな
り、逆に30重量％より多いと衝撃強さは高くなる
が透明性及び耐熱性は低下する。又、アセトン可
溶分の10重量％メチルエチルケトン溶液粘度が３
センチポイズより低いと組成物の衝撃強さが低く
なり、10センチポイズより高いと加工流動性が著
しく低下する。
組成物のアセトン分別とアセトン可溶分の10重
量％メチルエチルケトン溶液粘度は次のような手
順によつて測定を行なつた。
アセトンによる分別
乾燥した樹脂約１ｇを精秤してアセトン20ｇを
加え、25℃で５時間振盪する。その後20000rpm
で遠心分離することによつて不溶分と可溶分を分
離し、デカンテーシヨンにより可溶分を別の容器
に分け取る。不溶分に再度アセトン20ｇを加え、
25℃で１時間振盪後20000rpmで遠心分離し、デ
カンテーシヨンにより不溶分と可溶分に分ける。
可溶分は先の可溶分と合わせ過剰のメタノール中
へ滴下して凝固物を取り出し乾燥、計量する（Ｐ
ｇ）。又、不溶分も乾燥、計量する（Ｑｇ）。アセ
トン不溶分と可溶分の重量比は次の式を用いて計
算する。
アセトン不溶分＝Ｑ／Ｐ＋Ｑ×100（％）
アセトン可溶分＝Ｐ／Ｐ＋Ｑ×100（％）
10重量％メチルエチルケトン溶液粘度
乾燥したアセトン可溶分２ｇにメチルエチルケ
トン18ｇを加え、25℃で２時間振盪、溶解する。
この溶液を25℃でオストワルドキヤノンフエンス
ケ毛細管（No.200）を通して落下させ、液面が一
定の間隔にしるされた２本の標線間を通過する時
間（ｔ秒）を測定する。別途粘度既知の標準液を
用い粘度と落下秒数との換算係数（Ｋ）を求めて
おき、次の計算式によつて10重量％メチルエチル
ケトン溶液粘度を計算する。
10重量％メチルエチルケトン溶液粘度＝Ｋ×ｔ
（センチポイズ）
アセトン不溶分の屈折率ａと可溶分の屈折率ｂ
の差｜ａ−ｂ｜が0.005より大きい場合は透明性
が著しく低下する。更に｜ａ−ｂ｜0.002の範
囲が透明性の点で特に好ましい。
本発明の熱可塑性樹脂組成物は、ABS樹脂の
アセトン不溶分の屈折率がアセトン可溶分とメチ
ルメタクリレート共重合体との平均屈折率に一致
するような比率でABS樹脂とメチルメタクリレ
ート共重合体を混合することによつて得られる。
一般にアセトン不溶分の屈折率を直接測定する
ことは困難なので実質的にはABS樹脂及びその
アセトン可溶分の屈折率からアセトン不溶分の屈
折率を次の式によつて計算することができる。
ｆ−ｇ（１−ｍ）／ｍ。ただし、ABS樹脂の屈折率
をｆ、そのアセトン不溶分比率をｍ、アセトン可
溶分の比率と屈折率をそれぞれ１−ｍ、ｇとす
る。
同様の理由から本発明の組成物におけるアセト
ン不溶分の屈折率ａは次式で計算された値を使用
することが可能である。組成物の屈折率をｃ、そ
のアセトン不溶分比率をｐ、アセトン可溶分の比
率と屈折率をそれぞれ１−ｐ、ｂとすれば、
ａ＝ｃ−ｐ（１−ｐ）／ｐ。
本発明の要件を満足するABS樹脂はポリブタ
ジエン、或いはジエン系ゴムラテツクスの存在下
でアクリロニトリル、スチレン、α−メチルスチ
レンを乳化グラフト重合するか、乳化重合した
ABSグラフト重合体と塊状重合、溶液重合又は
懸濁重合したアクリロニトリル−スチレン−α−
メチルスチレン共重合体とを混合する方法で製造
するのが好ましい。又、メチルメタクリレート共
重合体は従来公知の塊状重合、溶液重合又は懸濁
重合によつて製造することができる。ABS樹脂
とメチルメタクリレート共重合体の混合は溶融状
態で行なうことが工業的に有利である。溶融混合
（混練）の方法は従来から使用されている装置が
利用できる。例えば、押出機、ニーダー、ロール
ミキサー、バンバリーミキサー等である。
本発明の組成物には本発明が目的とする特長を
失わせない範囲内で酸化防止剤、可塑剤、紫外線
吸収剤、難燃剤、顔料、染料、ガラス繊維等を添
加することができる。更に押出し成形、射出成形
等によつて所望の成形品を作ることが可能で、そ
の優れた透明性、衝撃強さ、耐熱性、耐薬品性等
を特長として自動車部品、工業部品、家電部品、
雑貨等広い用途分野へ展開できる。
以下に実施例を示す。部は重量部を表わす。
〔実施例〕
実施例 １
平均粒子径が0.1ミクロンであるポリブタジエ
ンラテツクスを固形分換算で30部とアクリロニト
リル19.6部、スチレン50.4部から開始剤を過硫酸
ナトリウム、連鎖移動剤をｔ−ドデシルメルカプ
タンとする乳化グラフト重合によつてグラフト率
22重量％の樹脂（Ａ−１）を得た。一方メチルメ
タクリレート92部とアクリロニトリル８部及びエ
チルベンゼン20部から開始剤をジクミルパーオキ
サイド、連鎖移動剤をｔ−ドデシルメルカプタン
とする溶液重合によつて共重合体（Ｂ−１）を得
た。
得られた樹脂（Ａ−１）55部と共重合体（Ｂ−
１）45部を二軸押出機により溶融混合、ペレツト
化した。このペレツトを用いて測定したアセトン
不溶分量は20.1重量％、アセトン可溶分の10重量
％メチルエチルケトン溶液粘度は6.1cps、又、ア
セトン不溶分の屈折率（n25 D）は1.525、アセトン
可溶分の屈折率は1.524であつた。
更に250℃の成形温度で射出成形して得た試験
片からアイゾツト衝撃強さと加熱変形温度を測定
するとともに厚さ1/8インチのプレートによつて
全光線透過率を測定した。同様にして樹脂（Ａ−
１）と共重合体（Ｂ−１）の混合比を変えてペレ
ツト化し、評価を行なつた。評価結果を表１に示
した。
本発明の組成物は高度の透明性とアイゾツト衝
撃強さを有し、しかも良好な耐熱性を示した。
[Industrial Field of Application] The present invention relates to a thermoplastic resin composition having high transparency and impact strength, as well as good heat resistance. [Prior art] Acrylonitrile-styrene copolymer is a thermoplastic resin that is hard, transparent, has excellent chemical resistance, and is also economical. Impact strength is often required. For this reason, impact strength has been improved by, for example, graft polymerizing acrylonitrile and styrene onto rubber. Such resins are known as ABS resins and are widely used today, but they usually lack the transparency characteristic of acrylonitrile-styrene copolymers and are opaque. If the particle size of the dispersed rubber is made sufficiently smaller than the wavelength of visible light, transparency will improve, but at the same time, impact strength will drop significantly. In order to impart transparency without impairing the inherent properties of ABS resin, it is necessary to match the refractive index of the dispersed particles and the refractive index of the continuous phase. Science and Technology, Supplements (Encyclopedia of Polymer
Science and Technology, Supplement) 1st
Vol. 307-318, Interscience, New York (1976). So-called MABS resins are known. this
MABS resin certainly has good transparency and impact strength, but on the other hand, it has been tested by Transactions of the Faraday Society, No.
56, 1529-1534 (1960), increasing the number of acrylonitrile-methyl methacrylate bonds significantly reduces heat resistance. Therefore, in Japanese Patent Publication No. 44-15902, styrene was replaced with α-methylstyrene, and by blending an acrylonitrile-α-methylstyrene-methyl methacrylate copolymer with a graft copolymer, a material with high heat resistance and good transparency was developed. Although a method for obtaining a resin composition has been introduced, the resulting resin has low processing fluidity, and large molded products or molded products with complex shapes are not only prone to yellowing but also difficult to obtain satisfactory transparency. The value is low. On the other hand, in Japanese Patent Publication No. 39-8667, polymethyl methacrylate and a graft copolymer are blended, but the rubber latex used for the graft copolymer has an extremely small particle size of 0.1 microns or less. The impact strength is insufficient, and since a large amount of a graft copolymer with low heat resistance is blended, the resulting composition still has low transparency and heat resistance. Furthermore, Japanese Patent Publication No. 55-7882 discloses a methyl methacrylate polymer (component A) containing 10% by weight or less of alkyl acrylate as a copolymerization component and an acrylonitrile-styrene polymer (component A) containing 12 to 22% by weight of acrylonitrile as a copolymerization component. Component B)
A graft copolymer (component C) obtained by graft polymerizing acrylonitrile and styrene to a rubber having a glass transition point of -30°C or lower is blended to match the refractive index of component C and the refractive index of components A and B. However, the acrylonitrile-styrene copolymer that is compatible with the methyl methacrylate resin must have an acrylonitrile content of around 15% by weight. The chemical resistance of the molding material is inferior to that of so-called ABS resin, and as seen in Examples (Tests 1 to 4), a large amount of component C, which has low heat resistance, is blended in order to increase the impact resistance of the molding material. Therefore, the heat resistance of the molding material is considered to be low. [Problems to be Solved by the Present Invention] The present inventors have attempted to obtain a highly transparent thermoplastic resin composition without impairing the excellent impact resistance originally possessed by ABS resin. A detailed study was conducted on two-component compositions with methacrylate copolymers. [Means for solving the problem] As a result, a copolymer of methyl methacrylate and acrylonitrile is commonly used in ABS.
It has been found that the resin is compatible with the resin, and that the impact strength of the resulting composition is dramatically improved compared to ABS resin with the same amount of rubber content. This fact has an important meaning for the purpose of the present invention, and it is possible to obtain a transparent thermoplastic resin having a certain impact strength by using rubber particles with a lower glass transition temperature than in the conventional method. Since the amount can be reduced, it is possible to further improve transparency and heat resistance. That is, the present invention consists of a copolymer of 22 to 35% by weight of acrylonitrile, 45 to 78% by weight of styrene, and 0 to 20% by weight of α-methylstyrene and polybutadiene, or a diene rubber containing 85% by weight or more of butadiene, Grafting rate is 10-40% by weight
ABS resin and methyl methacrylate 70-99% by weight
and a methyl methacrylate copolymer consisting of 1 to 20% by weight of acrylonitrile and 0 to 10% by weight of other copolymerizable monomers, in which (A) the amount of acetone insoluble matter in the composition is 5～
(B) The refractive index (n 25 D ) of the acetone-insoluble fraction is a,
The present invention relates to a thermoplastic resin composition characterized in that, where b is the refractive index of the acetone-soluble component, |a-b|≦0.005. [Effects of the Invention] The composition having the characteristics of the present invention has extremely high compatibility between the two components, and there is no dependence of transparency on the molding temperature, so even if the composition is large or has a complex shape, it can be used It is possible to obtain it easily. For example, as seen in JP-A No. 57-126812, it has been generally accepted that it is difficult to obtain a resin composition with excellent transparency and impact strength unless the grafting ratio of the graft polymer is sufficiently high. It was a way of thinking. However, in the present invention, the contradictory properties of transparency and impact strength can be simultaneously improved when the graft ratio of ABS resin is in the range of 10 to 40% by weight, and the fact that heat resistance can also be improved is proven in past literature and patents. This is a fact that could not have been predicted from the published publications and was revealed for the first time by the present invention. [Function] ABS constituting the thermoplastic resin composition of the present invention
It is necessary that the resin and the methyl methacrylate copolymer are polymers each having the above component composition. If the amount of acrylonitrile in the copolymer of ABS resin is less than 22% by weight, properties such as chemical resistance will deteriorate, and if it exceeds 35% by weight, thermal discoloration of the resulting composition will increase, which is not preferred.
When the amount of acrylonitrile is in the range of 25 to 33% by weight, a composition particularly excellent in transparency and impact strength can be obtained.
It is possible to further improve heat resistance by replacing part of the styrene in the copolymer with α-methylstyrene, but if the amount of α-methylstyrene is 20
If it exceeds % by weight, not only will the processing fluidity be reduced and the molded product become more likely to yellow, but also the transparency and impact strength will be reduced, making it impossible to achieve the object of the present invention. Also, the amount of butadiene in diene rubber is
If it is less than 85% by weight, impact strength will decrease. Examples of other monomers in an amount of 15% by weight or less include styrene, acrylonitrile, and the like.
If the grafting rate of the ABS resin is less than 10% by weight, the impact strength will decrease, and if it is more than 40% by weight, the transparency will decrease. Although the details of the reason why transparency decreases when the grafting ratio is greater than 40% by weight are unknown, according to the experimental results related to the present invention, the grafted acrylonitrile-styrene-α-methylstyrene copolymer has a It is presumed that this is because when the grafting rate is high, the dispersed rubber particles are substantially composed of two layers having different refractive indexes, since this affects the refractive index. Grafting rate is 20-35% by weight
Within this range, the dispersed rubber particles are uniformly dissolved in the composition, so that a composition having particularly high transparency and impact strength can be obtained. The grafting rate of ABS resin is determined by extracting the soluble content in acetone at room temperature, measuring the dry weight (u) of the remaining acetone-insoluble content, and comparing this weight with the polybutadiene or diene rubber used to manufacture the ABS resin. The difference between the weight (v) and the weight of the grafted monomer was calculated using the following formula. Grafting rate = u-v/v x 100 (%) Methyl methacrylate copolymer has a copolymerization component of acrylonitrile exceeding 20% by weight.
The compatibility with ABS resin deteriorates, and both the transparency and impact strength of the composition decrease. When the acrylonitrile content is in the range of 5 to 15% by weight, the compatibility with ABS resin becomes very high, and excellent transparency and impact strength can be obtained. Furthermore, examples of monomers copolymerizable with methyl methacrylate and acrylonitrile include styrene, methyl acrylate, and methacrylonitrile. The amount of acetone insoluble matter in the composition consisting of ABS resin and methyl methacrylate copolymer is 5 to 30% by weight. If it is less than 5% by weight, the impact strength will be low, and if it is more than 30% by weight, the impact strength will be low. Although it increases, transparency and heat resistance decrease. In addition, the viscosity of a 10% by weight methyl ethyl ketone solution soluble in acetone is 3.
If it is lower than centipoise, the impact strength of the composition will be low, and if it is higher than 10 centipoise, the processing fluidity will be significantly reduced. The acetone fractionation of the composition and the viscosity of a 10% by weight methyl ethyl ketone solution of the acetone soluble portion were measured by the following procedure. Fractionation with acetone Weigh accurately about 1 g of dried resin, add 20 g of acetone, and shake at 25°C for 5 hours. then 20000rpm
The insoluble and soluble components are separated by centrifugation, and the soluble components are separated into separate containers by decantation. Add 20g of acetone to the insoluble matter again,
After shaking at 25°C for 1 hour, centrifuge at 20,000 rpm and separate into insoluble and soluble components by decantation.
The soluble content is combined with the previous soluble content and dropped into excess methanol, and the coagulated product is taken out, dried, and weighed (P
g). Insoluble matter is also dried and weighed (Qg). The weight ratio of acetone insoluble and soluble components is calculated using the following formula. Acetone insoluble content = Q/P+Q x 100 (%) Acetone soluble content = P/P + Q x 100 (%) 10% by weight methyl ethyl ketone solution viscosity Add 18 g of methyl ethyl ketone to 2 g of dried acetone soluble content and shake at 25°C for 2 hours. , dissolve.
This solution is allowed to fall through an Ostwald Canon Fuenske capillary tube (No. 200) at 25°C, and the time (t seconds) it takes for the liquid level to pass between two marked lines marked at a constant interval is measured. Separately, use a standard solution with known viscosity to determine the conversion coefficient (K) between viscosity and falling seconds, and calculate the viscosity of the 10% by weight methyl ethyl ketone solution using the following formula. 10% by weight methyl ethyl ketone solution viscosity = K x t
(centipoise) Refractive index a of acetone insoluble portion and refractive index b of soluble portion
When the difference |a−b| is larger than 0.005, transparency is significantly reduced. Furthermore, the range of |a-b|0.002 is particularly preferable from the viewpoint of transparency. The thermoplastic resin composition of the present invention comprises ABS resin and methyl methacrylate copolymer in a ratio such that the refractive index of the acetone-insoluble portion of the ABS resin matches the average refractive index of the acetone-soluble portion and the methyl methacrylate copolymer. obtained by mixing. Since it is generally difficult to directly measure the refractive index of the acetone-insoluble component, the refractive index of the acetone-insoluble component can be calculated from the refractive index of the ABS resin and its acetone-soluble component using the following formula. f-g(1-m)/m. However, it is assumed that the refractive index of the ABS resin is f, its acetone-insoluble content ratio is m, and the acetone-soluble content ratio and refractive index are 1-m and g, respectively. For the same reason, the refractive index a of the acetone-insoluble component in the composition of the present invention can be calculated using the following formula. If the refractive index of the composition is c, its acetone-insoluble content ratio is p, and the acetone-soluble content ratio and refractive index are 1-p and b, respectively, then a=c-p(1-p)/p. The ABS resin that satisfies the requirements of the present invention is obtained by emulsion graft polymerization or emulsion polymerization of acrylonitrile, styrene, or α-methylstyrene in the presence of polybutadiene or diene rubber latex.
ABS graft polymer and acrylonitrile-styrene-α- polymerized in bulk, solution or suspension
It is preferable to manufacture by mixing with a methylstyrene copolymer. Furthermore, the methyl methacrylate copolymer can be produced by conventionally known bulk polymerization, solution polymerization or suspension polymerization. It is industrially advantageous to mix the ABS resin and methyl methacrylate copolymer in a molten state. For the melt mixing (kneading) method, conventionally used equipment can be used. For example, an extruder, a kneader, a roll mixer, a Banbury mixer, etc. Antioxidants, plasticizers, ultraviolet absorbers, flame retardants, pigments, dyes, glass fibers, and the like can be added to the composition of the present invention within a range that does not impair the characteristics aimed at by the present invention. Furthermore, it is possible to make desired molded products by extrusion molding, injection molding, etc., and its excellent transparency, impact strength, heat resistance, chemical resistance, etc. make it suitable for automobile parts, industrial parts, home appliance parts,
Can be used in a wide range of applications such as miscellaneous goods. Examples are shown below. Parts represent parts by weight. [Example] Example 1 30 parts of polybutadiene latex with an average particle size of 0.1 micron in terms of solid content, 19.6 parts of acrylonitrile, and 50.4 parts of styrene were mixed with sodium persulfate as an initiator and t-dodecyl mercaptan as a chain transfer agent. Grafting rate by emulsion graft polymerization
22% by weight of resin (A-1) was obtained. Separately, a copolymer (B-1) was obtained by solution polymerization of 92 parts of methyl methacrylate, 8 parts of acrylonitrile, and 20 parts of ethylbenzene using dicumyl peroxide as an initiator and t-dodecyl mercaptan as a chain transfer agent. 55 parts of the obtained resin (A-1) and copolymer (B-
1) 45 parts were melt-mixed and pelletized using a twin-screw extruder. The amount of acetone-insoluble content measured using this pellet was 20.1% by weight, the viscosity of a 10% by weight methyl ethyl ketone solution of the acetone-soluble content was 6.1 cps, and the refractive index (n 25 D ) of the acetone-insoluble content was 1.525, and the acetone-soluble content was 6.1 cps. Its refractive index was 1.524. Further, the Izot impact strength and heating deformation temperature were measured from test pieces obtained by injection molding at a molding temperature of 250°C, and the total light transmittance was measured using a 1/8 inch thick plate. Similarly, resin (A-
1) and the copolymer (B-1) were changed into pellets and evaluated. The evaluation results are shown in Table 1. The composition of the present invention had a high degree of transparency and Izod impact strength, and also exhibited good heat resistance.
【表】
実施例 ２
実施例１と同様に溶液重合でポリメチルメタク
リレート（Ｂ−２）、メチルメタクリレート90部
とメチルアクリレート２部、アクリロニトリル８
部から共重合体（Ｂ−３）、メチルメタクリレー
ト87部とアクリロニトリル13部から共重合体（Ｂ
−４）、そしてメチルメタクリレート78部とアク
リロニトリル22部から共重合体（Ｂ−５）を作
り、共重合体の屈折率から計算された混合比率に
従つてそれぞれ二軸押出機により樹脂（Ａ−１）
と溶融混合、ペレツト化した。得られたペレツト
の評価結果を表２に示した。
表２より樹脂（Ａ−１）と共重合体（Ｂ−２）
からなる組成物及び樹脂（Ａ−１）と共重合体
（Ｂ−５）からなる組成物の透明性はともに低い
ことがわかる。[Table] Example 2 Polymethyl methacrylate (B-2), 90 parts of methyl methacrylate, 2 parts of methyl acrylate, and 8 parts of acrylonitrile were subjected to solution polymerization in the same manner as in Example 1.
87 parts of methyl methacrylate and 13 parts of acrylonitrile to form a copolymer (B-3).
A copolymer (B-5) was made from 78 parts of methyl methacrylate and 22 parts of acrylonitrile, and the resin (A- 1)
The mixture was melt-mixed and pelletized. Table 2 shows the evaluation results of the obtained pellets. From Table 2, resin (A-1) and copolymer (B-2)
It can be seen that the transparency of both the composition consisting of the resin (A-1) and the copolymer (B-5) is low.
【表】
実施例 ３
平均粒子径が0.15ミクロンのブタジエン95重量
％とスチレン５重量％からなるゴムラテツクスを
固形分換算で60部とアクリロニトリル13.2部、ス
チレン26.8部から開始剤を過硫酸ナトリウム、連
鎖移動剤をｔ−ドデシルメルカプタンとする乳化
グラフト重合によつてグラフト率14重量％の樹脂
（Ａ−２）、グラフト率32％の樹脂（Ａ−３）、グ
ラフト率43％の樹脂（Ａ−４）を得た。又、アク
リロニトリル30部とスチレン70部及びエチルベン
ゼン20部から熱開始による溶液重合で共重合体
（Ｃ−１）を得た。表３に示した組成の樹脂（Ａ
−２）〜樹脂（Ａ−４）と共重合体（Ｂ−１）、
共重合体（Ｃ−１）をそれぞれ二軸押出機により
溶融混合、ペレツト化し評価を行なつた。[Table] Example 3 A rubber latex consisting of 95% by weight of butadiene and 5% by weight of styrene with an average particle size of 0.15 microns was mixed with 60 parts (in terms of solid content), 13.2 parts of acrylonitrile, and 26.8 parts of styrene, and an initiator was added to sodium persulfate and chain transferred. Resin with a graft ratio of 14% by weight (A-2), resin with a graft ratio of 32% (A-3), and resin with a graft ratio of 43% (A-4) by emulsion graft polymerization using t-dodecyl mercaptan as the agent. I got it. A copolymer (C-1) was also obtained by thermally initiated solution polymerization from 30 parts of acrylonitrile, 70 parts of styrene, and 20 parts of ethylbenzene. Resin with the composition shown in Table 3 (A
-2) ~Resin (A-4) and copolymer (B-1),
The copolymers (C-1) were melt-mixed using a twin-screw extruder, pelletized, and evaluated.
【表】
表３よりメチルエチルケトン不溶分量が本発明
の範囲より少ないとアイゾツト衝撃強さが逆に本
発明の範囲を超えると全光線透過率がそれぞれ低
下し、又、グラフト率が本発明の範囲を超えると
全光線透過率、アイゾツト衝撃強さがともに低下
することがわかる。[Table] Table 3 shows that if the amount of methyl ethyl ketone insoluble matter is less than the range of the present invention, the Izot impact strength will be lower than the range of the present invention, and if the total light transmittance is lower than the range of the present invention, the graft ratio will be lower than the range of the present invention. It can be seen that when the value exceeds the total light transmittance, both the total light transmittance and the Izot impact strength decrease.
Claims (1)
〜78重量％、α−メチルスチレン０〜20重量％の
共重合体とポリブタジエン、或いはブタジエンを
85重量％以上含有するジエン系ゴムからなり、グ
ラフト率が10〜40重量％であるABS樹脂と、メ
チルメタクリレート70〜99重量％及びアクリロニ
トリル１〜20重量％、その他の共重合可能な単量
体０〜10重量％からなるメチルメタクリレート共
重合体とから基本的になる組成物において、 (A) 組成物中のアセトン不溶分量が５〜30重量％
で、しかもアセトン可溶分の10重量％メチルエ
チルケトン溶液粘度が３〜10センチポイズであ
り、 (B) アセトン不溶分の屈折率（n25 D）をａ、アセ
トン可溶分の屈折率をｂとして、 ｜ａ−ｂ｜≦0.005 の範囲であることを特徴とする熱可塑性樹脂組成
物。 ２ ABS樹脂がアクリロニトリル25〜33重量％、
スチレン67〜75重量％の共重合体とポリブタジエ
ン、或いはブタジエンを85重量％以上含有するジ
エン系ゴムからなり、グラフト率が20〜35重量％
である特許請求の範囲第１項記載の熱可塑性樹脂
組成物。 ３ メチルメタクリレート共重合体がメチルメタ
クリレート85〜95重量％及びアクリロニトリル５
〜15重量％からなる特許請求の範囲第１項記載の
熱可塑性樹脂組成物。 ４ メチルメタクリレート共重合体を構成するそ
の他の共重合可能な単量体がメチルアクリレート
である特許請求の範囲第１項記載の熱可塑性樹脂
組成物。 ５ メチルメタクリレート共重合体を構成するそ
の他の共重合可能な単量体がスチレンである特許
請求の範囲第１項記載の熱可塑性樹脂組成物。 ６ メチルメタクリレート共重合体を構成するそ
の他の共重合可能な単量体がメタクリロニトリル
である特許請求の範囲第１項記載の熱可塑性樹脂
組成物。 ７ ｜ａ−ｂ｜≦0.002 の範囲である特許請求の範囲第１項記載の熱可塑
性樹脂組成物。[Claims] 1 22-35% by weight of acrylonitrile, 45% by weight of styrene
~78% by weight, α-methylstyrene 0-20% by weight copolymer and polybutadiene, or butadiene
ABS resin consisting of diene rubber containing 85% by weight or more and a graft ratio of 10 to 40% by weight, 70 to 99% by weight of methyl methacrylate, 1 to 20% by weight of acrylonitrile, and other copolymerizable monomers. In a composition basically consisting of a methyl methacrylate copolymer consisting of 0 to 10% by weight, (A) the amount of acetone insoluble matter in the composition is 5 to 30% by weight;
Moreover, the viscosity of the 10% by weight methyl ethyl ketone solution of the acetone-soluble component is 3 to 10 centipoise, (B) the refractive index (n 25 D ) of the acetone-insoluble component is a, and the refractive index of the acetone-soluble component is b, A thermoplastic resin composition characterized in that |a-b|≦0.005. 2 ABS resin contains 25-33% by weight of acrylonitrile,
Consists of a copolymer containing 67 to 75% by weight of styrene and polybutadiene, or a diene rubber containing at least 85% by weight of butadiene, with a grafting rate of 20 to 35% by weight.
The thermoplastic resin composition according to claim 1. 3. Methyl methacrylate copolymer contains 85-95% by weight of methyl methacrylate and 5% acrylonitrile.
The thermoplastic resin composition according to claim 1, comprising ~15% by weight. 4. The thermoplastic resin composition according to claim 1, wherein the other copolymerizable monomer constituting the methyl methacrylate copolymer is methyl acrylate. 5. The thermoplastic resin composition according to claim 1, wherein the other copolymerizable monomer constituting the methyl methacrylate copolymer is styrene. 6. The thermoplastic resin composition according to claim 1, wherein the other copolymerizable monomer constituting the methyl methacrylate copolymer is methacrylonitrile. 7. The thermoplastic resin composition according to claim 1, which is within the range of |a-b|≦0.002.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14258284A JPS6121152A (en) | 1984-07-10 | 1984-07-10 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14258284A JPS6121152A (en) | 1984-07-10 | 1984-07-10 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6121152A JPS6121152A (en) | 1986-01-29 |
| JPS6352054B2 true JPS6352054B2 (en) | 1988-10-17 |
Family
ID=15318655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14258284A Granted JPS6121152A (en) | 1984-07-10 | 1984-07-10 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6121152A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62183230U (en) * | 1986-05-07 | 1987-11-20 | ||
| JPH07103295B2 (en) * | 1987-03-31 | 1995-11-08 | 住友ダウ株式会社 | Thermoplastic resin composition excellent in color development |
| JPH086006B2 (en) * | 1988-05-02 | 1996-01-24 | 株式会社小糸製作所 | Automotive lighting |
| KR100384383B1 (en) * | 1998-06-03 | 2003-08-14 | 주식회사 엘지화학 | Manufacturing method of thermoplastic resin |
| KR20000014173A (en) * | 1998-08-18 | 2000-03-06 | 성재갑 | Thermoplastic resin composition and method for preparing it |
| KR20000039470A (en) * | 1998-12-14 | 2000-07-05 | 성재갑 | Thermoplastic composition and method of preparing thereof |
| EP3632981B1 (en) * | 2017-06-01 | 2021-04-07 | Toray Industries, Inc. | Thermoplastic resin composition, production method for thermoplastic resin composition, molded article, and production method for molded article |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4834828A (en) * | 1971-09-24 | 1973-05-22 | ||
| JPS5063057A (en) * | 1973-03-03 | 1975-05-29 |
-
1984
- 1984-07-10 JP JP14258284A patent/JPS6121152A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4834828A (en) * | 1971-09-24 | 1973-05-22 | ||
| JPS5063057A (en) * | 1973-03-03 | 1975-05-29 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6121152A (en) | 1986-01-29 |
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