JPS6247208B2 - - Google Patents
Info
- Publication number
- JPS6247208B2 JPS6247208B2 JP16386879A JP16386879A JPS6247208B2 JP S6247208 B2 JPS6247208 B2 JP S6247208B2 JP 16386879 A JP16386879 A JP 16386879A JP 16386879 A JP16386879 A JP 16386879A JP S6247208 B2 JPS6247208 B2 JP S6247208B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- graft
- resin
- polymerization
- graft polymerization
- 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
- 239000000203 mixture Substances 0.000 claims description 44
- 238000010559 graft polymerization reaction Methods 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 31
- 229920003244 diene elastomer Polymers 0.000 claims description 20
- -1 alkenyl aromatic compound Chemical class 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 11
- 150000008360 acrylonitriles Chemical class 0.000 claims description 6
- 229920000578 graft copolymer Polymers 0.000 claims description 6
- 229920000126 latex Polymers 0.000 claims description 5
- 239000004816 latex Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 description 51
- 239000011347 resin Substances 0.000 description 51
- 238000000034 method Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 13
- 229920001971 elastomer Polymers 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 229920000800 acrylic rubber Polymers 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 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 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Description
本発明は、耐衝撃性、硬度及び加工性のすぐれ
た耐候性熱可塑性樹脂の製造法に関する。
更に詳言すれば、少量のジエン系ゴムラテツク
スの存在下にアルケニル芳香族化合物とビニルシ
アン化合物またはメタクリル酸エステルとの混合
物をグラフト重合（一次グラフト重合）させ、次
いでアクリル酸アルキルエステルと少量のビニル
シアン化合物またはメタクリル酸エステルの混合
物をグラフト重合（二次グラフト重合）させるこ
とにより、かかる樹脂を製造する方法を提供する
ものである。
従来ポリスチレン、アクリロニトリル−スチレ
ン樹脂などの熱可塑性樹脂は、衝撃強度が劣つて
いるため、ジエン系ゴムと機械的にブレンドした
り、ジエン系ゴムにグラフト重合させることによ
りその欠点を改良している。しかし、ジエン系ゴ
ムで強化した樹脂は耐衝撃性にすぐれるが、ゴム
成分中に多くの二重結合を含んでいるため、耐候
性が良好とは言えず、そのため用途が制限される
ことになる。
これに対しアクリルゴムなどの非ジエン系ゴム
で強化した樹脂は、二重結合を殆ど含まないので
耐候性はすぐれるが、スチレン、アクリロニトリ
ルなどのビニル単量体がグラフトしにくく、耐衝
撃性のすぐれた樹脂は得難い。そこで、アクリル
ゴムなどの非ジエン系ゴムにビニル単量体を効果
的にグラフト重合させるために、予めゴムを酸
素、過酸化物などにより酸化処理するかまたはジ
ビニルベンゼンなどの架橋性モノマーでゲル化さ
せるかあるいはアクリルゴムの重合時にブタジエ
ンなどのジエン系モノマーを少量共重合させるな
どにより、ゴムを前処理する方法が提案されてき
た。しかしながら、これらの方法は重合工程が複
雑であり、得られる重合体は再現性に乏しく、ま
た工業化も容易ではない。この欠点を改良する方
法として、特公昭47−47863ではジエン系重合体
の存在下にアクリル酸アルキルエステルと架橋性
モノマーの混合物をグラフト重合させ、しかるの
ちビニル単量体の混合物をグラフト重合させる方
法が提案されている。
この方法は、前述した前処理方法に比べ重合工
程が簡単であり、工業化が容易である。しかし、
樹脂の性質として耐衝撃性は有するが、一方、加
工性、硬度のすぐれた樹脂が得られにくい。樹脂
が軟かいと耐衝撃性にすぐれていても、成形加工
して使用するとき成形品にきずがついたり変形し
たりして、商品価値を下げることになり、樹脂の
用途が制限される。また、樹脂の加工性は、成形
加工工程における重要な特性であり、加工性が悪
いと成形加工の生産効率が低下し、使用にあたつ
て用途が制限される。
本発明者らは、かかる欠点を改良するため種々
検討した結果、ジエン系ゴムの存在下に一次グラ
フト重合として重合させた場合、硬い性質を示す
アルケニル芳香族化合物とビニルシアン化合物、
またはメタクリル酸エステルから選ばれた単量体
との混合物を、二次グラフト重合の活性点を残し
てジエン系ゴムにグラフト重合させ、しかるのち
二次グラフト重合として重合させた場合、ゴム状
の性質を示すアクリル酸アルキルエステルとビニ
ルシアン化合物またはメタクリル酸エステルから
選ばれた単量体との混合物をグラフト重合させる
ことにより、耐衝撃性と硬度そして加工性のすぐ
れた樹脂が得られることを見出した。
本発明は、このような知見に基づいてなされた
ものである。すなわち本発明は、ジエン系ゴムラ
テツクス５〜30重量部（固形分として）の存在下
にアルケニル芳香族化合物40〜90重量％とビニル
シアン化合物またはメタクリル酸エステルより選
ばれた少なくとも１種の単量体60〜10重量％から
なる単量体混合物(A)95〜70重量部をグラフト重合
させてグラフト率10〜100重量％のグラフト重合
体を得、しかるのちこの生成グラフト重合体100
重量部に炭素数２〜８のアルキル基をもつアクリ
ル酸アルキルエステル80〜95重量％とビニルシア
ン化合物またはメタクリル酸エステルより選ばれ
た少なくとも１種の単量体20〜５重量％からなる
単量体混合物(B)５〜60重量部を加えてグラフト重
合を行い、ジエン系ゴムに対して単量体混合物(B)
を10重量％以上のグラフト率でグラフト重合させ
ることを特徴とする耐衝撃性、硬度及び加工性の
すぐれた耐候性熱可塑性樹脂の製造法を提供する
ものである。
本発明に使用するジエン系ゴムとしては、ポリ
ブタジエン、ブタジエン−スチレン共重合体、ブ
タジエン−アクリロニトリル共重合体、ポリイソ
プレンなどであり、２種以上を混合使用してもよ
い。ジエン系ゴムを使用する目的は、ジエン系ゴ
ムにまずビニル単量体混合物(A)をグラフト重合さ
せ、しかるのちアクリル酸アルキルエステルを主
成分とする単量体混合物(B)をグラフト重合させる
に際し、ジエン系ゴムをバインダーとしてビニル
単量体混合物(A)の重合体とアクリル酸アルキルエ
ステルを主成分とする単量体混合物(B)のゴム状重
合体を間接的に化学的結合をもたせることにあ
る。この化学的結合は、ジエン系ゴムに対するグ
ラフト率を測定することで確認された。ジエン系
ゴムの使用量が５重量合部未満であると得られた
樹脂は層状はくり現象がおこり、またすぐれた耐
衝撃性が得られない。一方、30重量部をこえると
樹脂が軟かくなり、また耐候性が悪くなり好まし
くない。
本発明において一次グラフト重合に使用するア
ルケニル芳香族化合物とは、スチレン、アルフア
メチルスチレンなどであり、２種以上混合して使
用しても良い。ビニルシアン化合物とは、アクリ
ロニトリル、メタクリロニトリルなどであり、ま
たメタクリル酸エステルはメタクリル酸メチル、
メタクリル酸エチル、メタクリル酸ブチルなどで
あり、これらは２種以上混合して使用することも
可能である。
一次グラフト重合に使用する単量体混合物中の
アルケニル芳香族化合物は40重量％未満であると
流動性、色調が低下する。一方、90重量％をこえ
ると耐油性が劣り好ましくない。
本発明の一次グラフト重合のグラフト率が10重
量％未満であると、得られた樹脂は耐衝撃性が劣
り、また層状はくり現象がみられ好ましくない。
一方、100重量％をこえると二次グラフト重合に
おいて単量体混合物(B)のグラフト重合がおこりに
くくなり、得られた樹脂は耐衝撃性が劣り、また
層状はくり現象がみられ好ましくない。
一次グラフト重合及び二次グラフト重合におけ
るグラフト率は次の方法によつて求める。
グラフト重合体ラテツクスをメタノール中に少
量づつ撹拌しながら添加し、ポリマーを析出回収
し、そしてメタノールで充分洗滌し乾燥させる。
この乾燥サンプル２ｇを精秤し、アセトン100ｇ
を加え24時間室温で振とう撹拌する。撹拌後、遠
心分離機を用いて可溶分と下溶分に分離し、不溶
分を乾燥精秤する。
次式に従つてグラフト率を算出する。
グラフト率（％）＝アセトン不溶分（ｇ）−仕込み乾燥サンプル中のジエン系ゴム量（ｇ）／仕込み乾燥サンプル
中のジエン系ゴム量（ｇ）×100
本発明の二次グラフト重合において用いる炭素
数２〜８のアルキル基をもつアクリル酸エステル
とは、アクリル酸エチル、アクリル酸プロピル、
アクリル酸ｎ−ブチル、アクリル酸イソブチル、
アクリル酸ペンチル、アクリル酸ヘキシル、アク
リル酸ｎ−オクチル、アクリル酸２−エチルヘキ
シルなどであり、アルキル基は直鎖状でも分枝し
た鎖状でも良い。また、これらの単量体は単独あ
るいは混合して使用することができる。また、ビ
ニルシアン化合物とは、例えばアクリロニトリ
ル、メタクリロニトリルなどであり、メタクリル
酸エステルとは、例えばメタクリル酸メチル、メ
タクリル酸エチルなどであり、単独あるいは混合
して使用することができる。ビニルシアン化合物
またはメタクリル酸エステルから選ばれた単量体
の使用量が５重量％未満であると二次グラフト重
合時のグラフト率が低く、得られた樹脂は耐衝撃
性が劣り、また層状はくり現象がおこり好ましく
ない。一方、アクリル酸アルキルエステルは、耐
衝撃性の向上を目的に添加しているため、アクリ
ル酸アルキルエステルと共重合させるビニルシア
ン化合物とメタクリル酸エステルの合計量が20重
量％をこえると、得られた樹脂は耐衝撃性が低下
し、好ましくない。
本発明の二次グラフト重合に使用する単量体混
合物の使用量が、一次グラフト重合で得たグラフ
ト重合体100重量部に対し５重量部未満であると
耐衝撃性のすぐれた樹脂が得られず、一方60重量
部をこえると得られた樹脂の硬度が低下し、また
層状はくり現象がおこり好ましくない。
本発明の二次グラフト重合におけるグラフト率
が10重量％未満であると得られた樹脂は耐衝撃性
が低下し、また層状はくり現象がおこり好ましく
ない。
本発明においては、グラフト率が大きな役割を
果たすが、その調節方法については種々の方法が
採用できる。例えば、連鎖移動剤の使用量、開始
剤の種類及び使用量、重合温度、単量体をグラフ
ト重合させるときの添加方法などの条件を適宜選
ぶことによつてグラフト率を任意に調節すること
が可能である。一次及び二次グラフト重合に用い
る乳化重合の助剤は、通常使用されているものを
使用することができ、特に制限はない。
連鎖移動剤としては、例えばｔ−ドデシルメル
カプタン、四塩化炭素などがある。乳化剤として
は、通常の陰イオン界面活性剤、非イオン界面活
性剤または陽イオン界面活性剤を使用することが
できる。開始剤としては、公知の過酸化物、酸化
還元系開始剤、アゾ化合物などが使用できる。更
に、グラフト重合時に架橋剤として、例えばジビ
ニルベンゼンを少量使用することも可能である。
本発明で得られた樹脂は、単独でまたは他の樹
脂またはゴムとブレンドして使用できる。ブレン
ドする他の樹脂またはゴムとしては、本発明の樹
脂と相溶性のある樹脂またはゴムが好ましく、例
えば塩化ビニル系樹脂、ABS樹脂、AS樹脂、塩
素化ポリエチレン、NBR、クロロプレンゴムな
どがあり、用途により２種以上混用することがで
きる。本発明の樹脂単独または他の樹脂、ゴムと
のブレンド使用において添加剤を使用することが
できる。添加剤としては、紫外線吸収剤、滑剤、
充填剤、帯電防止剤、熱安定性向上剤、可塑剤、
着色剤などを任意に加えるこてができる。
本発明の樹脂または他の樹脂ゴムとブレンドし
た組成物は、射出成形、シート押出成形、異形押
出成形、パイプ押出成形、真空成形、ブロー成形
などの成形法で成形することができる。
次に、実施例を挙げて本発明を更に具体的に説
明するが、本発明はその要旨をこえない限り、こ
れらの実施例に制約されるものではない。
以下に示した部及び％は、特に断らない限り、
重量部及び重量％を意味する。
実施例 １
The present invention relates to a method for producing a weather-resistant thermoplastic resin having excellent impact resistance, hardness, and processability. More specifically, a mixture of an alkenyl aromatic compound and a vinyl cyanide compound or a methacrylic acid ester is graft-polymerized (primary graft polymerization) in the presence of a small amount of diene rubber latex, and then a mixture of an acrylic acid alkyl ester and a small amount of vinyl cyanide is graft-polymerized. The present invention provides a method for producing such a resin by graft polymerizing (secondary graft polymerization) a mixture of compounds or methacrylic acid esters. Conventionally, thermoplastic resins such as polystyrene and acrylonitrile-styrene resins have poor impact strength, so their drawbacks have been improved by mechanically blending them with diene rubbers or graft polymerizing them with diene rubbers. However, although resin reinforced with diene rubber has excellent impact resistance, the rubber component contains many double bonds, so it cannot be said to have good weather resistance, which limits its applications. Become. On the other hand, resins reinforced with non-diene rubber such as acrylic rubber contain almost no double bonds and have excellent weather resistance, but they are difficult to graft with vinyl monomers such as styrene and acrylonitrile, and have poor impact resistance. Excellent resin is difficult to obtain. Therefore, in order to effectively graft-polymerize vinyl monomers onto non-diene rubber such as acrylic rubber, the rubber must be oxidized with oxygen, peroxide, etc., or gelled with a crosslinking monomer such as divinylbenzene. Methods have been proposed in which rubber is pretreated by, for example, copolymerizing a small amount of diene monomers such as butadiene during polymerization of acrylic rubber. However, these methods require complicated polymerization steps, the resulting polymers have poor reproducibility, and industrialization is not easy. As a method to improve this drawback, Japanese Patent Publication No. 47-47863 proposed a method in which a mixture of an acrylic acid alkyl ester and a crosslinking monomer was graft-polymerized in the presence of a diene polymer, and then a mixture of vinyl monomers was graft-polymerized. is proposed. This method has a simpler polymerization step than the pretreatment method described above, and is easy to industrialize. but,
Although the resin has impact resistance, it is difficult to obtain a resin with excellent processability and hardness. If the resin is soft, even if it has excellent impact resistance, when it is molded and used, the molded product will be scratched or deformed, lowering its commercial value and limiting the uses of the resin. Further, the processability of the resin is an important characteristic in the molding process, and if the processability is poor, the production efficiency of the molding process will decrease, and the applications of the resin will be limited. As a result of various studies to improve these drawbacks, the present inventors have discovered that alkenyl aromatic compounds and vinyl cyanide compounds exhibit hard properties when polymerized as primary graft polymerization in the presence of a diene rubber.
Alternatively, when a mixture with a monomer selected from methacrylic acid esters is graft-polymerized onto a diene rubber leaving active sites for secondary graft polymerization, and then polymerized as secondary graft polymerization, rubber-like properties can be obtained. It has been discovered that a resin with excellent impact resistance, hardness, and processability can be obtained by graft polymerizing a mixture of an acrylic acid alkyl ester and a monomer selected from vinyl cyanide compounds or methacrylic acid esters. . The present invention has been made based on such knowledge. That is, the present invention comprises 40 to 90 weight % of an alkenyl aromatic compound and at least one monomer selected from a vinyl cyanide compound or a methacrylic acid ester in the presence of 5 to 30 parts by weight (as solid content) of a diene rubber latex. 95 to 70 parts by weight of a monomer mixture (A) consisting of 60 to 10% by weight is graft-polymerized to obtain a graft polymer with a graft ratio of 10 to 100% by weight, and then the resulting graft polymer is 100% by weight.
A monomer consisting of 80 to 95% by weight of an acrylic acid alkyl ester having an alkyl group having 2 to 8 carbon atoms and 20 to 5% by weight of at least one monomer selected from vinyl cyanide compounds or methacrylic esters. Graft polymerization is carried out by adding 5 to 60 parts by weight of the monomer mixture (B) to the diene rubber.
The present invention provides a method for producing a weather-resistant thermoplastic resin having excellent impact resistance, hardness, and processability, which is characterized by graft polymerizing the following at a graft ratio of 10% by weight or more. The diene rubber used in the present invention includes polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, polyisoprene, etc., and two or more types may be used as a mixture. The purpose of using the diene rubber is to first graft-polymerize the vinyl monomer mixture (A) onto the diene-based rubber, and then graft-polymerize the monomer mixture (B) whose main component is an acrylic acid alkyl ester. , to indirectly create a chemical bond between the polymer of the vinyl monomer mixture (A) and the rubber-like polymer of the monomer mixture (B) whose main component is an alkyl acrylate ester using a diene rubber as a binder. It is in. This chemical bond was confirmed by measuring the grafting rate to the diene rubber. If the amount of diene rubber used is less than 5 parts by weight, the resulting resin will suffer from layer peeling phenomenon and will not have excellent impact resistance. On the other hand, if it exceeds 30 parts by weight, the resin becomes soft and weather resistance deteriorates, which is not preferable. In the present invention, the alkenyl aromatic compounds used in the primary graft polymerization include styrene, alphamethylstyrene, etc., and two or more thereof may be used as a mixture. Vinyl cyanide compounds include acrylonitrile, methacrylonitrile, etc., and methacrylic acid esters include methyl methacrylate,
These include ethyl methacrylate and butyl methacrylate, and it is also possible to use a mixture of two or more of these. If the alkenyl aromatic compound in the monomer mixture used in the primary graft polymerization is less than 40% by weight, fluidity and color tone will deteriorate. On the other hand, if it exceeds 90% by weight, oil resistance will be poor and undesirable. If the grafting ratio in the primary graft polymerization of the present invention is less than 10% by weight, the resulting resin will have poor impact resistance and a layer peeling phenomenon will occur, which is not preferable.
On the other hand, if it exceeds 100% by weight, graft polymerization of the monomer mixture (B) becomes difficult to occur in the secondary graft polymerization, and the resulting resin has poor impact resistance and layer peeling phenomenon is observed, which is not preferable. The graft ratio in primary graft polymerization and secondary graft polymerization is determined by the following method. The graft polymer latex is added little by little to methanol with stirring, the polymer is precipitated and recovered, and then thoroughly washed with methanol and dried.
Accurately weigh 2g of this dry sample and add 100g of acetone.
Add and stir at room temperature for 24 hours. After stirring, the mixture is separated into soluble and sub-soluble components using a centrifugal separator, and the insoluble components are dried and precisely weighed. Calculate the grafting rate according to the following formula. Grafting ratio (%) = Acetone insoluble content (g) - Amount of diene rubber in the prepared dry sample (g) / Amount of diene rubber in the prepared dry sample (g) x 100 Carbon used in the secondary graft polymerization of the present invention Acrylic esters having 2 to 8 alkyl groups include ethyl acrylate, propyl acrylate,
n-butyl acrylate, isobutyl acrylate,
Examples include pentyl acrylate, hexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate, and the alkyl group may be linear or branched. Moreover, these monomers can be used alone or in combination. Further, the vinyl cyanide compound is, for example, acrylonitrile, methacrylonitrile, etc., and the methacrylic acid ester is, for example, methyl methacrylate, ethyl methacrylate, etc., and they can be used alone or in combination. If the amount of the monomer selected from vinyl cyanide compounds or methacrylic acid esters is less than 5% by weight, the grafting rate during secondary graft polymerization will be low, the resulting resin will have poor impact resistance, and the layered structure will be poor. This is undesirable as it causes a hollowing phenomenon. On the other hand, since acrylic acid alkyl ester is added for the purpose of improving impact resistance, if the total amount of vinyl cyanide compound and methacrylic acid ester to be copolymerized with acrylic acid alkyl ester exceeds 20% by weight, the obtained A resin that has a low impact resistance is undesirable. When the amount of the monomer mixture used in the secondary graft polymerization of the present invention is less than 5 parts by weight based on 100 parts by weight of the graft polymer obtained in the primary graft polymerization, a resin with excellent impact resistance can be obtained. On the other hand, if it exceeds 60 parts by weight, the hardness of the resulting resin decreases and layer peeling phenomenon occurs, which is not preferable. If the graft ratio in the secondary graft polymerization of the present invention is less than 10% by weight, the resulting resin will have a lower impact resistance and a layer peeling phenomenon will occur, which is not preferable. In the present invention, the grafting ratio plays a major role, and various methods can be used to adjust it. For example, the grafting ratio can be adjusted arbitrarily by appropriately selecting conditions such as the amount of chain transfer agent used, the type and amount of initiator used, polymerization temperature, and the method of adding monomers during graft polymerization. It is possible. As the emulsion polymerization aid used in the primary and secondary graft polymerization, commonly used ones can be used, and there are no particular limitations. Examples of chain transfer agents include t-dodecylmercaptan and carbon tetrachloride. As emulsifiers it is possible to use customary anionic, nonionic or cationic surfactants. As the initiator, known peroxides, redox initiators, azo compounds, etc. can be used. Furthermore, it is also possible to use small amounts of divinylbenzene, for example, as a crosslinking agent during the graft polymerization. The resin obtained in the present invention can be used alone or blended with other resins or rubbers. The other resin or rubber to be blended is preferably a resin or rubber that is compatible with the resin of the present invention, such as vinyl chloride resin, ABS resin, AS resin, chlorinated polyethylene, NBR, chloroprene rubber, etc. Two or more types can be used in combination. Additives can be used in the resin of the present invention alone or in blends with other resins and rubbers. Additives include ultraviolet absorbers, lubricants,
Fillers, antistatic agents, thermal stability improvers, plasticizers,
A trowel can be used to optionally add colorants, etc. The resin of the present invention or a composition blended with other resin rubbers can be molded by a molding method such as injection molding, sheet extrusion molding, profile extrusion molding, pipe extrusion molding, vacuum molding, or blow molding. Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded. The parts and percentages shown below are unless otherwise specified.
Parts and percentages by weight are meant. Example 1
【表】
表−１に示した組成〔〕をリアクターに仕込
み、窒素置換した後、重合温度70℃で２時間にわ
たつて〔〕を連続添加し重合を行つた。重合転
化率（ポリマー収率）は97〜98％であつた。一次
グラフト重合終了後直ちに組成〔〕を３時間に
わたつて連続添加し重合を行つた。重合転化率は
97〜98％であつた。得られた重合体ラテツクスに
硫酸を加え、加熱して凝固分離水洗乾燥により乾
燥粉体を得た。得られた樹脂の物性を表−４に示
す。
実施例 ２
表−１の(ハ)の組成において、組成〔〕の重合
時の連続添加時間を実施例１の２時間から５時間
に延長した以外は、実施例１と同様に行つた。得
られた樹脂(ニ)の物性を表−４に示す。
参考例 １
（本発明範囲外の単量体の添加順序で行なつた
例）
実施例１の表−１の(ロ)の組成で〔〕と〔〕
の添加順序を逆にしてグラフト重合させたもの
で、組成〔〕と組成〔〕の添加順序をかえた
以外は実施例１と同様にして行つた。得られた樹
脂(ホ)の物性を表−４に示す。重合体(ホ)は、本発明
の範囲外の重合方法によつて得られた樹脂であ
り、加工性、硬度のすぐれたものが得られず好ま
しくない。
参考例 ２
（本発明範囲外のジエン系ゴムの使用量で行つ
た例）
実施例１の一次グラフト重合組成〔〕，〔〕
において、ポリブタジエン及び単量体を表−２に
示した組成に変更した。この組成以外は、実施例
１の(イ)と同様にして行つた。得られた樹脂の物性
を表−４に示す。重合体(ヘ)は、ポリブタジエン量
が本発明の範囲より少ない樹脂であり、層状はく
り現象がみられる。
一方、重合体(ト)は、ポリブタジエン量が本発明
の範囲より多い樹脂であり、硬度が低く好ましく
ない。[Table] The composition [] shown in Table 1 was charged into a reactor, the atmosphere was purged with nitrogen, and then [] was continuously added for 2 hours at a polymerization temperature of 70°C to carry out polymerization. The polymerization conversion rate (polymer yield) was 97-98%. Immediately after completion of the primary graft polymerization, composition [] was continuously added for 3 hours to carry out polymerization. The polymerization conversion rate is
It was 97-98%. Sulfuric acid was added to the obtained polymer latex, heated, solidified, separated, washed with water, and dried to obtain a dry powder. Table 4 shows the physical properties of the obtained resin. Example 2 In the composition (c) of Table 1, the same procedure as in Example 1 was carried out except that the continuous addition time during polymerization of composition [] was extended from 2 hours in Example 1 to 5 hours. Table 4 shows the physical properties of the resin (d) obtained. Reference Example 1 (Example in which monomers were added in an order outside the range of the present invention) With the composition of (b) in Table 1 of Example 1, [] and []
The graft polymerization was carried out in the same manner as in Example 1 except that the order of addition of composition [] and composition [] was reversed. Table 4 shows the physical properties of the resin (e) obtained. Polymer (e) is a resin obtained by a polymerization method outside the scope of the present invention, and is not preferred because it does not provide excellent processability and hardness. Reference Example 2 (Example carried out using an amount of diene rubber outside the range of the present invention) Primary graft polymerization composition of Example 1 [], []
In this case, the compositions of polybutadiene and monomers were changed to those shown in Table 2. Except for this composition, the same procedure as in Example 1 (a) was carried out. Table 4 shows the physical properties of the obtained resin. Polymer (f) is a resin in which the amount of polybutadiene is less than the range of the present invention, and a layer peeling phenomenon is observed. On the other hand, polymer (g) is a resin in which the amount of polybutadiene is higher than the range of the present invention, and has low hardness, which is not preferable.
【表】
参考例 ３
（二次グラフト重合組成のアクリル酸アルキル
エステルの組成割合が本発明範囲外の例）
表−１の(ロ)の組成〔〕における単量体を表−
３に示した組成に変更した。これ以外は、実施例
１の(ロ)と同様に行つた。得られた樹脂の物性を表
−４に示す。重合体(チ)は、二次グラフト重合組成
中のアクリル酸アルキルエステルと共重合するビ
ニル単量体量が本発明の範囲より少ない樹脂であ
り、層状はくり現象を示し、耐衝撃性も低く好ま
しくない。一方、重合体（リ）は、ビニル単量体
量が本発明の範囲より多い樹脂であり、耐衝撃性
が低く好ましくない。[Table] Reference Example 3 (Example where the composition ratio of acrylic acid alkyl ester in the secondary graft polymerization composition is outside the scope of the present invention)
The composition was changed to that shown in 3. Other than this, the same procedure as in Example 1 (b) was carried out. Table 4 shows the physical properties of the obtained resin. Polymer (H) is a resin in which the amount of vinyl monomer copolymerized with the acrylic acid alkyl ester in the secondary graft polymerization composition is smaller than the range of the present invention, exhibits a layer peeling phenomenon, and has low impact resistance. Undesirable. On the other hand, polymer (Li) is a resin in which the amount of vinyl monomer is larger than the range of the present invention, and has low impact resistance, which is not preferable.
【表】
参考例 ４
（二次グラフト重合のグラフト率が本発明範囲
外の例）
表−１の(ロ)の組成において、組成〔〕をリア
クターに一括添加して重合した以外は、実施例１
と同様に行つた。得られた樹脂（ヌ）の物性を表
−４に示した。重合体（ヌ）は、二次グラフト重
合のグラフト率が本発明の範囲より低い樹脂であ
り、層状はくり現象を示し、また耐衝撃性も低く
好ましくない。
参考例 ５
（一次グラフト重合のグラフト率を本発明範囲
外とした例）
表−１の(ロ)の組成において、一次グラフト重合
を下記条件で行つた。これ以外は、実施例１と同
様に行つた。
重合体（ル）；一次グラフト重合組成〔〕を
〔〕に一括して加え重合を行つ
た。
重合体（オ）；一次グラフト重合組成〔〕を10
時間にわたつて連続添加し、重合を
行つた。
得られた樹脂（ヌ），（ル）の物性を表−４に示
す。重合体（ル）は、一次グラフト重合における
グラフト率が本発明の範囲より低い樹脂であり、
耐衝撃性が低く、また層状はくり現象がみられ
る。
一方、重合体（オ）は、グラフト率が本発明の
範囲より高い樹脂であり、耐衝撃性が低く、また
層状はくり現象がみられ好ましくない。[Table] Reference Example 4 (Example where the graft ratio of secondary graft polymerization is outside the scope of the present invention) In the composition (b) of Table 1, except that the composition [] was added all at once to the reactor and polymerized, the examples 1
I went in the same way. The physical properties of the obtained resin (N) are shown in Table 4. Polymer (N) is a resin whose graft ratio in secondary graft polymerization is lower than the range of the present invention, exhibits a layer peeling phenomenon, and has low impact resistance, which is not preferable. Reference Example 5 (Example in which the graft ratio in primary graft polymerization was outside the range of the present invention) In the composition (b) of Table 1, primary graft polymerization was performed under the following conditions. Other than this, the same procedure as in Example 1 was carried out. Polymer (L): Primary graft polymerization composition [] was added all at once to [] to carry out polymerization. Polymer (e); primary graft polymerization composition [] 10
Polymerization was carried out by continuous addition over a period of time. The physical properties of the obtained resins (N) and (R) are shown in Table 4. The polymer (R) is a resin whose graft ratio in primary graft polymerization is lower than the range of the present invention,
Impact resistance is low and layer peeling phenomenon is observed. On the other hand, polymer (e) is a resin having a graft ratio higher than the range of the present invention, has low impact resistance, and exhibits a layer peeling phenomenon, which is not preferable.
【表】
物性測定法の説明
加工性；高化式フローテスターを用いて200℃に
加熱した樹脂に30Kg／cm2の荷重をかけたとき直径
１mm、長さ２mmのノズルより１秒間に流出する樹
脂の体積を表わしたものである。
アイゾツト衝撃強度；ASTM D256
ロツクウエル硬度 ；ASTM D785
層状はくり現象；射出成形によつて得たダンベ
ルのテストピースを折り曲げ、層状はくり現象を
目視判定した。
〇印＝層状はくりなし、または少ない。
×印＝層状はくりあり。
実施例 ３
（本発明品の耐候性テスト結果）
本発明の方法で得られた樹脂の促進耐候テスト
をABS樹脂及びAAS樹脂を比較に行なつた。
テスト方法は、紫外線カーボンアークウエザメ
ータを使用し、ASTM−D1435の条件で行つた。
結果を表−５に示す。[Table] Description of physical property measurement method Processability: When a load of 30Kg/ cm2 is applied to resin heated to 200℃ using a Koka flow tester, it flows out in 1 second from a nozzle with a diameter of 1mm and a length of 2mm. It represents the volume of resin. Izot impact strength; ASTM D256 Rockwell hardness; ASTM D785 Layer peeling phenomenon: A dumbbell test piece obtained by injection molding was bent and the layer peeling phenomenon was visually determined. 〇 mark = No or few layers. ×=Layer peeling. Example 3 (Weather resistance test results of products of the present invention) Accelerated weather resistance tests of resins obtained by the method of the present invention were conducted to compare ABS resin and AAS resin. The test method was carried out using an ultraviolet carbon arc weather meter under the conditions of ASTM-D1435.
The results are shown in Table-5.
【表】【table】
Claims (1)
分として）の存在下にアルケニル芳香族化合物40
〜90重量％とビニルシアン化合物またはメタクリ
ル酸エステルより選ばれた少なくとも１種の単量
体60〜10重量％からなる単量体混合物(A)95〜70重
量部をグラフト重合させて、グラフト率10〜100
重量％のグラフト重合体を得、次いでこの生成グ
ラフト重合体100重量部に炭素数２〜８のアルキ
ル基をもつアクリル酸アルキルエステル80〜95重
量％とビニルシアン化合物またはメタクリル酸エ
ステルより選ばれた少なくとも１種の単量体20〜
５重量％からなる単量体混合物(B)５〜60重量部を
加えてグラフト重合を行い、ジエン系ゴムに対し
て単量体混合物(B)を10重量％以上のグラフト率で
グラフト重合させることを特徴とする耐候性熱可
塑性樹脂の製造法。1 40 parts by weight of an alkenyl aromatic compound in the presence of 5 to 30 parts by weight (as solid content) of diene rubber latex
Graft polymerization of 95 to 70 parts by weight of a monomer mixture (A) consisting of ~90% by weight and 60 to 10% by weight of at least one monomer selected from vinyl cyanide compounds or methacrylic acid esters to obtain a graft ratio 10~100
% by weight of a graft polymer was obtained, and then 100 parts by weight of the resulting graft polymer was added with 80 to 95 weight % of an acrylic acid alkyl ester having an alkyl group having 2 to 8 carbon atoms and a vinyl cyanide compound or a methacrylic acid ester selected from At least one monomer20~
Graft polymerization is performed by adding 5 to 60 parts by weight of a monomer mixture (B) consisting of 5% by weight, and graft polymerization of the monomer mixture (B) to the diene rubber at a graft ratio of 10% by weight or more. A method for producing a weather-resistant thermoplastic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16386879A JPS5686918A (en) | 1979-12-17 | 1979-12-17 | Preparation of weather-resistant thermoplastic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16386879A JPS5686918A (en) | 1979-12-17 | 1979-12-17 | Preparation of weather-resistant thermoplastic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5686918A JPS5686918A (en) | 1981-07-15 |
| JPS6247208B2 true JPS6247208B2 (en) | 1987-10-07 |
Family
ID=15782291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16386879A Granted JPS5686918A (en) | 1979-12-17 | 1979-12-17 | Preparation of weather-resistant thermoplastic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5686918A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02128406U (en) * | 1989-03-30 | 1990-10-23 |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4504605A (en) * | 1982-12-20 | 1985-03-12 | The Standard Oil Company | Film-forming olefinic nitrile polymer latex and method of preparing same |
| JP2853987B2 (en) * | 1996-01-29 | 1999-02-03 | 奇美実業股▲分▼有限公司 | Method for producing styrenic resin |
| EP0985692B1 (en) * | 1998-09-09 | 2005-01-19 | Rohm And Haas Company | Improved MBS impact modifier |
| US8969476B2 (en) | 2002-06-21 | 2015-03-03 | Sabic Global Technologies B.V. | Impact-modified compositions |
| US20040225034A1 (en) * | 2003-05-09 | 2004-11-11 | General Electric Company | Impact-modified compositions and method |
-
1979
- 1979-12-17 JP JP16386879A patent/JPS5686918A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02128406U (en) * | 1989-03-30 | 1990-10-23 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5686918A (en) | 1981-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6247208B2 (en) | ||
| JP2016528358A (en) | Heat resistant styrene copolymer and styrene resin composition containing the same | |
| US4594387A (en) | Thermoplastic resin composition having toughness and high thermal deformation resistance | |
| JPH0791341B2 (en) | Maleimide-based copolymer and method for producing the same | |
| JP3283461B2 (en) | Rubber modified styrenic resin composition | |
| JPH0243762B2 (en) | ||
| JP4327198B2 (en) | Thermoplastic resin composition | |
| US4701495A (en) | Thermoplastic resin composition | |
| JPH0530861B2 (en) | ||
| JP3286971B2 (en) | Styrene-based copolymer, thermoplastic resin composition containing the copolymer, and methods for producing them | |
| JP2524367B2 (en) | ABS molding composition with low residual butadiene content | |
| JP3626288B2 (en) | Low rigidity styrenic resin composition with excellent pigment dispersibility | |
| JP2508192B2 (en) | Process for producing N-arylmaleimide copolymer | |
| US6136918A (en) | Rubber latexes, graft copolymers, and thermoplastic resin compositions | |
| JPH0356589B2 (en) | ||
| JPH0379386B2 (en) | ||
| US3875259A (en) | Thermoplastic resin-graft polyblend compositions | |
| JPH08151417A (en) | Impact-resistant high-nitrile polymer and its production | |
| JPS6346781B2 (en) | ||
| JPS636081B2 (en) | ||
| US3870769A (en) | Thermoplastic resin-graft-polyblend compositions | |
| US3531548A (en) | Two-step polymerization processes for the production of high impact abstype resins | |
| JP3516226B2 (en) | Rubber-rich MABS resin composition and rubber-modified thermoplastic resin composition | |
| JP2854697B2 (en) | Method for producing high nitrile polymer composition | |
| KR900008716B1 (en) | Thermoplastic resin composition |