JPS6365105B2 - - Google Patents
Info
- Publication number
- JPS6365105B2 JPS6365105B2 JP19026582A JP19026582A JPS6365105B2 JP S6365105 B2 JPS6365105 B2 JP S6365105B2 JP 19026582 A JP19026582 A JP 19026582A JP 19026582 A JP19026582 A JP 19026582A JP S6365105 B2 JPS6365105 B2 JP S6365105B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- copolymer
- parts
- monomer
- unsaturated nitrile
- 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 54
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 32
- 150000002825 nitriles Chemical class 0.000 claims description 19
- 239000004816 latex Substances 0.000 claims description 18
- 229920000126 latex Polymers 0.000 claims description 18
- 239000011342 resin composition Substances 0.000 claims description 18
- 229920000578 graft copolymer Polymers 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 13
- 229920000515 polycarbonate Polymers 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 2
- 239000000839 emulsion Substances 0.000 claims 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 24
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- -1 alkyl styrene Chemical compound 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229920002857 polybutadiene Polymers 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 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
- 159000000000 sodium salts Chemical class 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical class CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- MWCZYBGQYVKRTG-UHFFFAOYSA-N CC(O)=O.CC(O)=O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O Chemical compound CC(O)=O.CC(O)=O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O MWCZYBGQYVKRTG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- UGUYQBMBIJFNRM-UHFFFAOYSA-N but-2-en-2-ylbenzene Chemical compound CC=C(C)C1=CC=CC=C1 UGUYQBMBIJFNRM-UHFFFAOYSA-N 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、熱分解性の少ない耐熱性耐衝撃性樹
脂組成物に関する。
ABS樹脂で代表されるゴム強化スチレン系樹
脂、ポリカーボネート、およびそれら混合物は、
耐衝撃性、耐熱性に優れる樹脂として従来から広
く用いられている。また、これらの樹脂において
は、α−メチルスチレン−アクリロニトリル共重
合体を配合することにより耐熱性がさらに改善さ
れることが古くから知られている。
α−メチルスチレン−アクリロニトリル共重合
体を配合した上述の耐熱性樹脂においては、α−
メチルスチレン含有量の増加と共に耐熱性は向上
するが、その反面、成形加工等の加熱時に熱分解
を起こしやすいといつた欠点を有している。さら
に、α−メチルステレンは反応性が悪く、α−メ
チルスチレンを70重量％以上含有するα−メチル
スチレン−アクリロニトリル共重合体を得るのも
困難である。
本発明者等は、α−メチルスチレン−アクリロ
ニトリル共重合体を配合した樹脂組成物の耐熱性
ならびに熱分解性を改良すべく鋭意研究した結
果、全単量体添加終了時における重合系内の未反
応不飽和ニトリル濃度をある一定濃度以上になる
ように単量体を調整しながら添加し、かつ、共重
合体ラテツクス粒子の90％以上が0.1μ以下となる
ように重合させたα−アルキルスチレン−不飽和
ニトリル共重合体を(A)とグラフト重合体(B)とから
なる組成物（第１の発明）が、耐熱性、耐衝撃
性、加工性ならびに、耐熱分解性に優れること、
および、該共重合体(A)、グラフト重合体(B)ならび
にポリカーボネート(C)とからなる組成物（第２の
発明）が、さらにそれら特性において優れること
を見出し本発明に到達した。
以下に本発明の耐熱性耐衝撃性樹脂組成物につ
いて詳細に説明する。
本発明におけるα−アルキルスチレン−不飽和
ニトリル共重合体を構成するα−アルキルスチレ
ンとは、下記一般式で示される化合物である。
（R1はC1〜C3のアルキル基であり、R2は水素、
C1〜C3のアルキル基またはハロゲン化アルキル
基である。）
α−メチレンスチレン、α−エチルスチレン、
メチル−α−メチルスチレン等が例示されるが、
好ましくはα−メチルスチレンである。
不飽和ニトリルとしては、アクリロニトリル、
メタクリロニトリル、エタクリロニトリル等が例
示されるが、好ましくはアクリロニトリルであ
る。
また、共重合時用いられるラジカル性開始剤と
しては、過硫酸カリウム、過硫酸ナトリウム、過
硫酸アンモニウムやキユメンハイドロパーオキサ
イド、ジイソプロピルベンゼンハイドロパーオキ
サイドのレドツクス等が例示されるが、好ましく
は過硫酸カリウム、過硫酸ナトリウムである。乳
化剤としては常用の乳化剤が使用できるが、好ま
しくはアニオン系乳化剤であり、ラウリル酸ナト
リウム、オレイン酸カリウム、オレイン酸ナトリ
ウム、脂肪酸のカリウムまたはナトリウム塩、ロ
ジン酸のカリウムまたはナトリウム塩、およびア
ルキルベンゼンスルホン酸ナトリウム等が例示さ
れる。
共重合体を構成するα−アルキルスチレンと不
飽和ニトリルの組成比は、α−アルキルスチレン
70〜80重量％および不飽和ニトリル30〜20重量％
である。
α−アルキルスチレンが70重量％未満であると
得られた共重合体の耐熱性は著しく劣り好ましく
ない。また80重量％を超えると重合終了時の未反
応単量体が多く、生産性が低下し好ましくない。
また、本発明において重要なことは、共重合体
が、全単量体添加終了時における重合系内の未反
応不飽和ニトリル濃度（単量体添加終了時の重合
系内の全未反応単量体に基づく）が31重量％以上
となるように調整して単量体を添加し、かつ、共
重合体ラテツクス粒子の90％以上が0.10μ以下と
なるように重合し、得られた共重合体であること
である。粒子径は重合終了時における共重合体ラ
テツクス粒子径を意味する。
単量体添加終了時における重合系内の未反応不
飽和ニトリル濃度が31重量％未満であると、重合
終了時の未反応単量体が多く、生産性が著しく低
下する。
重合系内の未反応不飽和ニトリル濃度が31重量
％以上となるように単量体を添加す具体的な調整
方法としては、重合系内のかかる濃度を測定しな
がらα−アルキルスチレンと不飽和ニトリルのそ
れぞれの添加速度を調整する方法、添加されるα
−アルキルスチレンと不飽和ニトリル混合単量体
の混合比率を調整する方法、さらには、α−アル
キルスチレンを全量仕込み、かかる濃度が31重量
％以上となるよう不飽和ニトリルの添加速度を調
整する方法等が例示される。
さらに、重合終了時の共重合体ラテツクス粒子
の90％以上を0.10μ以下にする必要がある。
0.10μを超えると生成共重合体を成形加工等で
加熱した時、熱分解が激しくなつてくる。
更に重合時の重合速度が遅くなり生成ラテツク
ス中に凝固物を生成し、かつ、未反応単量体が多
くなる。
共重合体自身優れた耐熱分解性を有しており、
50％重量減少の温度が370℃以上であることが特
に好ましい。
共重合体ラテツクス粒子の90％を0.10μ以下に
する具体的方法は、重合時使用する脱イオン水量
を多く使用したり、乳化剤量を多く使用する等で
ある。
α−アルキルスチレンと不飽和ニトリルの重合
系への添加方法には特に制限はなく、連続的、分
割的に添加してもよい。
さらに必要に応じて重合度調節剤等を加えても
よい。
上述の特定重合技術によつて得られた共重合体
を用いることによつて、耐熱性ならびに耐熱分解
性に優れた樹脂組成物が得られる。従来の重合技
術であるα−アルキルスチレンと不飽和ニトリル
を一括して重合系へ導入し、反応してなる共重合
体では、目的とする耐熱性ならびに耐熱分解性に
優れた樹脂組成物を得ることは困難である。
次に、グラフト重合体と構成するゴム質重合体
とは、ポリブタジエン、ブタジエン−スチレン共
重合体、プタジエン−アクリロニトリル共重合体
等の共役ジエン系ゴム、エチレン−プロピレン共
重合体、エチレン−プロピレン−ジエン共重合体
等のオレフイン系ゴム、ポリアクリル酸エステル
等のアクリル系ゴムなどが挙げられる。芳香族ビ
ニル化合物としては、スチレン、α−メチルスチ
レン、α−クロルスチレン、ビニルトルエンなど
挙げられ、特にスチレンが好ましい。シアン化ビ
ニル化合物としては、アクリロニトリル、メタア
クリロニトリルなどが挙げられ、特にアクリロニ
トリルが好ましい。さらに、他の重合性単量体化
合物としては、メチル、エチル、プロピル、ブチ
ル、ベンジル、ヘキシルなどのアクリル酸エステ
ル化合物およびメタアクリル酸エステル化合物な
どが挙げられ、特にメタアクリル酸メチルが好ま
しい。
ゴム質重合体とグラフト重合用単量体との組成
比には特に制限はないが、ゴム質重合体10〜70重
量％、単量体90〜30重量％が好ましい。さらにグ
ラフト重合用単量体に占める各単量体の比率にも
制限はないが、芳香族ビニル化合物50〜80重量
％、シアン化ビニル化合物および／または他の重
合性単量体化合物50〜20重量％が好ましい。
グラフト重合体を作る方法としては、公知の方
法がすべて利用できる。たとえば懸濁重合法、塊
状重合法、乳化重合法、溶液重合法などである。
本発明の第２発明において用いられるポリカー
ボネート樹脂としては、芳香族ポリカーボネー
ト、脂肪族ポリカーボネート、脂肪族−芳香族ポ
リカーボネート等々を挙げることができる。一般
には、2.2−ビス（４−オキシフエニル）アルカ
ン系、ビス（４−オキシフエニル）エーテル系、
ビス（４−オキシフエニル）スルホン、スルフイ
ド又はスルホキサイド系などのビスフエノール類
からなる重合体、もしくは共重合体であり、目的
に応じてハロゲンで置換されたビスフエノール類
を用いた重合体である。
本発明（第１の発明）の樹脂組成物は、上述の
共重合体20〜80重量％とグラフト重合体80〜20重
量％からなる。共重合体が20重量％未満（又はグ
ラフト重合体が80重量％を超す。）では、加工性、
耐熱性が劣り好ましくない。一方、共重合体が80
重量％を超すと（グラフト重合体が20重量％未
満）、耐衝撃性に劣り好ましくない。
又、本発明（第２の発明）の樹脂組成物は、上
述の共重合体10〜50重量％、グラフト重合体10〜
50重量％およびポリカーボネート30〜60重量％か
らなる。かかる組成範囲の樹脂組成物は、第１の
発明の樹脂組成物よりも優れた物性を有する。な
お、ポリカーボネートが60重量％を超すと物性バ
ランスが悪化する。
共重合体、グラフト重合体およびポリカーボネ
ートとの混合方法としては、押出機、バンバリー
ミキサー等を用いた公知方法が用いられる。
なお、混合に際して公知の安定剤、帯電防止
剤、滑剤、染顔料などの添加剤を適宜配合しても
よい。
以下に実施例を挙げて説明するが、本発明はこ
れらによつて何ら制限されるものでない。
実施例１および比較例１
共重合体およびグラフト重合体を表−１に示す
割合にて混練し（バンバリーミキサー、260℃、
４分間）、樹脂組成物を得た。樹脂組成物の物性
を表−２に示す。
用いられた共重合体（Ａ−１〜−４）およびグ
ラフト重合体（Ｂ−１〜−２）は以下の方法にて
重合された。
なお、熱分解性測定のためペレツト状樹脂組成
物より平板（100×200×３mm）を射出成形（290
℃）した。
−共重合体（Ａ−１）−
窒素置換した反応器に脱イオン水180重量部、
ラウリル硫酸ナトリウム３重量部、過硫酸カリウ
ム0.7重量部およびｎ−ドデシルメルカプタン0.1
重量部を加え、70℃に加熱した後、α−メチルス
チレン75重量部とアクリロニトリル10重量部から
なる単量体混合物の50％を添加し２時間に亘り重
合を行い更に残りの50％を３時間に亘り連続添加
した。
次に重合系内の未反応アクリロニトリル濃度を
調整しながらα−メチルスチレン３重量部および
アクリロニトリル12重量部を２時間に亘り添加し
た。
単量体添加終了時の重合系内の未反応アクリロ
ニトリル濃度は35重量％であつた。
単量体添加終了後、さらに２時間重合を継続し
た。
重合終了後の結果は以下のとおりであつた。
未反応α−メチルスチレン※１ ：0.59重量％
未反応アクリロニトリル※１ ：0.19重量％
共重合体ラテツクス中の凝集物量 ：0.002重量％
共重合体ラテツクスの平均粒子径※２ ：0.08μ
共重合体の軟化点※３ ：135℃
50％重量減少時の熱分解温度 ：379℃
−共重合体（Ａ−２）−
窒素置換した反応器に脱イオン水200重量部、
ラウリル硫酸ナトリウム３重量部、過硫酸カリウ
ム0.7重量部およびｎ−ドデシルメルカプタン0.1
重量部を加えた後、さらに、α−メチルスチレン
71重量部とアクリロニトリル20重量部からなる単
量体混合物の20重量％を加え、70℃に加熱し１時
間重合した後、かかる単量体混合物の残部（80重
量％）を４時間に亘り連続的に添加した。
次に重合系内の未反応アクリロニトリル濃度を
調整しながらα−メチルスチレン２重量部および
アクリロニトリル７重量部を２時間に亘り添加し
た。
単量体添加終了時の重合系内の未反応アクリロ
ニトリル濃度は43重量％であつた。
単量体添加終了後、さらに２時間重合を継続し
た。
重合終了後の結果は以下のとおりであつた。
未反応α−メチルスチレン ：0.29重量％
未反応アクリロニトリル ：0.16重量％
共重合体ラテツクス中の凝集物量 ：0.002重量％
共重合体ラテツクスの平均粒子径 ：0.050μ
共重合体の軟化点 ：129℃
50％重量減少時の熱分解温度 ：392℃
−共重合体（Ａ−３）−
窒素置換した反応器に脱イオン水200重量部、
ラウリル硫酸ナトリウム３重量部、過硫酸カリウ
ム0.7重量部およびｎ−ドデシルメルカプタン0.1
重量部を加え、70℃に加熱した後、α−メチルス
チレン78重量部とアクリロニトリル22重量部から
なる単量体混合物の20％を添加し、１時間重合し
た後、残りの80％を４時間にわたつて連続的に添
加した。
単量体添加終了時の重合系内の未反応アクリロ
ニトリル濃度は18重量％であつた。
単量体添加終了後、さらに２時間重合を継続し
た。
重合終了後の結果は以下のとおりであつた。
未反応α−メチルスチレン ：7.8重量％
未反応アクリロニトリル ：0.06重量％
共重合体ラテツクス中の凝集物量 ：0.09重量％
共重合体ラテツクス中の平均粒子径 ：0.08μ
共重合体の軟化点 ：102℃
50％重量減少時の熱分解温度 ：360℃
−共重合体（Ａ−４）−
窒素置換した反応器に脱イオン水120重量部、
ラウリル硫酸ナトリウム2.0重量部、過硫酸カリ
ウム0.7重量部およびｎ−ドデシルメルカプタン
0.1重量部を加えた後、さらに、α−メチルスチ
レン75重量部とアクリロニトリル10重量部とから
なる単量体混合物の20重量％を加え、70℃に加熱
し１時間重合した後、かかず単量体混合物の残部
（80重量％）を４時間に亘り連続的に添加した。
次に重合系内の未反応アクリロニトリル濃度を
調整しながらα−メチルスチレン３重量部および
アクリロニトリル12重量部を２時間にわたつて連
続的に添加した。
添加後の重合系内の未反応アクリロニトリル濃
度は32重量％であつた。単量体添加終了後、さら
に２時間重合を継続した。
重合終了後の結果は以下のとおりであつた。。
未反応α−メチルスチレン ：0.77重量％
未反応アクリロニトリル ：0.23重量％
共重合体ラテツクス中の凝集物量 ：0.42重量％
共重合体ラテツクス中の平均粒子径 ：0.13μ
共重合体の軟化点 ：134℃
50％重量減少時の熱分解温度 ：345℃
−グラフト重合体（Ｂ−１）−
窒素置換した反応器にポリブタジエンラテツク
ス60重量部（固形分）、脱イオン水200重量部、エ
チレンジアミン四酢酸二ナトリウム塩0.1重量部、
硫酸第２鉄0.001重量部、ナトリウムホルムアル
デヒドスルホキシレート0.4重量部を入れ、60℃
に加熱後アクリロニトリル13重量部、スチレン27
重量部およびキユメンハイドロパーオキサイド
0.2重量部からなる混合物を３時間に亘り連続的
に添加し、更に60℃で２時間重合した。
−グラフト重合体（Ｂ−２）−
ポリブタジエンラテツクス60重量部を30重量部
に、アクリロニトリル13重量部を20重量部に、又
スチレン27重量部を50重量部に変更した以外は、
グラフト重合体Ｂ−１と同様にして重合した。
The present invention relates to a heat-resistant, impact-resistant resin composition with low thermal decomposition properties. Rubber-reinforced styrenic resins such as ABS resin, polycarbonate, and mixtures thereof are
It has been widely used as a resin with excellent impact resistance and heat resistance. Furthermore, it has been known for a long time that the heat resistance of these resins can be further improved by incorporating an α-methylstyrene-acrylonitrile copolymer. In the above heat-resistant resin containing α-methylstyrene-acrylonitrile copolymer, α-
Heat resistance improves as the methylstyrene content increases, but on the other hand, it has the disadvantage of being susceptible to thermal decomposition during heating during molding and the like. Furthermore, α-methylstyrene has poor reactivity, and it is difficult to obtain an α-methylstyrene-acrylonitrile copolymer containing 70% by weight or more of α-methylstyrene. As a result of intensive research aimed at improving the heat resistance and thermal decomposition properties of resin compositions containing α-methylstyrene-acrylonitrile copolymer, the present inventors found that α-alkylstyrene added while adjusting the monomer so that the concentration of reactive unsaturated nitrile is above a certain concentration, and polymerized so that 90% or more of the copolymer latex particles have a particle size of 0.1 μ or less - The composition (first invention) comprising the unsaturated nitrile copolymer (A) and the graft polymer (B) has excellent heat resistance, impact resistance, processability, and thermal decomposition resistance;
The present inventors have also discovered that a composition (second invention) comprising the copolymer (A), graft polymer (B), and polycarbonate (C) is even more excellent in these properties, and has thus arrived at the present invention. The heat-resistant and impact-resistant resin composition of the present invention will be explained in detail below. The α-alkylstyrene constituting the α-alkylstyrene-unsaturated nitrile copolymer in the present invention is a compound represented by the following general formula. (R 1 is a C 1 to C 3 alkyl group, R 2 is hydrogen,
It is a C1 - C3 alkyl group or a halogenated alkyl group. ) α-methylene styrene, α-ethyl styrene,
Examples include methyl-α-methylstyrene,
α-methylstyrene is preferred. Examples of unsaturated nitriles include acrylonitrile,
Examples include methacrylonitrile and ethacrylonitrile, with acrylonitrile being preferred. Examples of the radical initiator used during copolymerization include potassium persulfate, sodium persulfate, ammonium persulfate, kyumene hydroperoxide, and diisopropylbenzene hydroperoxide redox, but potassium persulfate is preferred. , sodium persulfate. As the emulsifier, commonly used emulsifiers can be used, but anionic emulsifiers are preferred, such as sodium laurate, potassium oleate, sodium oleate, potassium or sodium salts of fatty acids, potassium or sodium salts of rosin acids, and alkylbenzenesulfonic acids. Examples include sodium. The composition ratio of α-alkylstyrene and unsaturated nitrile constituting the copolymer is
70-80% by weight and 30-20% by weight of unsaturated nitriles
It is. If the α-alkylstyrene content is less than 70% by weight, the resulting copolymer will have significantly poor heat resistance, which is not preferred. Moreover, if it exceeds 80% by weight, there will be a large amount of unreacted monomer at the end of polymerization, resulting in a decrease in productivity, which is not preferable. In addition, what is important in the present invention is that the copolymer has a concentration of unreacted unsaturated nitriles in the polymerization system at the end of all monomer addition ( The copolymer obtained by adding a monomer so that the particle size (based on the size of It is a combination. The particle size means the copolymer latex particle size at the end of polymerization. If the concentration of unreacted unsaturated nitrile in the polymerization system at the end of monomer addition is less than 31% by weight, there will be a large amount of unreacted monomer at the end of polymerization, resulting in a significant decrease in productivity. A specific adjustment method for adding a monomer so that the concentration of unreacted unsaturated nitrile in the polymerization system is 31% by weight or more is to measure the concentration of unreacted unsaturated nitrile in the polymerization system while How to adjust the respective addition rate of nitrile, α added
- A method of adjusting the mixing ratio of alkyl styrene and unsaturated nitrile mixed monomer, and a method of charging the entire amount of α-alkylstyrene and adjusting the rate of addition of unsaturated nitrile so that the concentration is 31% by weight or more. etc. are exemplified. Furthermore, it is necessary that at least 90% of the copolymer latex particles at the end of polymerization be 0.10μ or less. If it exceeds 0.10μ, thermal decomposition will become more intense when the resulting copolymer is heated during molding, etc. Furthermore, the polymerization rate during polymerization becomes slow, coagulates are formed in the produced latex, and unreacted monomers increase. The copolymer itself has excellent heat decomposition resistance,
It is particularly preferred that the temperature at which the weight decreases by 50% is 370°C or higher. Specific methods for making 90% of the copolymer latex particles 0.10μ or less include using a large amount of deionized water during polymerization, using a large amount of emulsifier, etc. There is no particular restriction on the method of adding α-alkylstyrene and unsaturated nitrile to the polymerization system, and they may be added continuously or in portions. Furthermore, a degree of polymerization regulator or the like may be added if necessary. By using the copolymer obtained by the above-mentioned specific polymerization technique, a resin composition having excellent heat resistance and heat decomposition resistance can be obtained. Using conventional polymerization technology, α-alkylstyrene and unsaturated nitrile are introduced into the polymerization system all at once and reacted to produce a copolymer, which yields a resin composition with excellent heat resistance and thermal decomposition resistance. That is difficult. Next, the rubbery polymers constituting the graft polymer include conjugated diene rubbers such as polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene copolymer, and ethylene-propylene-diene copolymer. Examples include olefin rubbers such as copolymers, and acrylic rubbers such as polyacrylic esters. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, α-chlorostyrene, and vinyltoluene, with styrene being particularly preferred. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. Further, other polymerizable monomer compounds include acrylic ester compounds and methacrylic ester compounds such as methyl, ethyl, propyl, butyl, benzyl, and hexyl, and methyl methacrylate is particularly preferred. The composition ratio of the rubbery polymer and the monomer for graft polymerization is not particularly limited, but preferably 10 to 70% by weight of the rubbery polymer and 90 to 30% by weight of the monomer. Furthermore, there is no limit to the proportion of each monomer in the monomers for graft polymerization, but aromatic vinyl compounds 50 to 80% by weight, vinyl cyanide compounds and/or other polymerizable monomer compounds 50 to 20% by weight. Weight percent is preferred. All known methods can be used to make the graft polymer. Examples include suspension polymerization, bulk polymerization, emulsion polymerization, and solution polymerization. Examples of the polycarbonate resin used in the second aspect of the present invention include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like. Generally, 2.2-bis(4-oxyphenyl)alkane type, bis(4-oxyphenyl)ether type,
It is a polymer or copolymer made of bisphenols such as bis(4-oxyphenyl)sulfone, sulfide, or sulfoxide, and is a polymer using bisphenols substituted with halogen depending on the purpose. The resin composition of the present invention (first invention) consists of 20 to 80% by weight of the above-mentioned copolymer and 80 to 20% by weight of the graft polymer. If the copolymer is less than 20% by weight (or the graft polymer is more than 80% by weight), processability,
It is not preferred because of its poor heat resistance. On the other hand, copolymer has 80
If the amount exceeds 20% by weight (less than 20% by weight of the graft polymer), the impact resistance will be poor and this is not preferable. Further, the resin composition of the present invention (second invention) contains 10 to 50% by weight of the above-mentioned copolymer and 10 to 50% by weight of the graft polymer.
50% by weight and 30-60% by weight of polycarbonate. A resin composition having such a composition range has better physical properties than the resin composition of the first invention. Note that if the content of polycarbonate exceeds 60% by weight, the physical property balance will deteriorate. As a method for mixing the copolymer, graft polymer, and polycarbonate, a known method using an extruder, Banbury mixer, etc. is used. In addition, known additives such as stabilizers, antistatic agents, lubricants, dyes and pigments may be appropriately added during mixing. Examples will be described below, but the present invention is not limited thereto. Example 1 and Comparative Example 1 The copolymer and graft polymer were kneaded in the proportions shown in Table 1 (Banbury mixer, 260°C,
4 minutes) to obtain a resin composition. Table 2 shows the physical properties of the resin composition. The copolymers (A-1 to -4) and graft polymers (B-1 to -2) used were polymerized by the following method. In order to measure thermal decomposition, a flat plate (100 x 200 x 3 mm) was injection molded (290 x 3 mm) from the pellet-like resin composition.
℃). -Copolymer (A-1)- 180 parts by weight of deionized water was added to a reactor purged with nitrogen.
3 parts by weight of sodium lauryl sulfate, 0.7 parts by weight of potassium persulfate, and 0.1 part by weight of n-dodecylmercaptan.
After adding parts by weight and heating to 70°C, 50% of a monomer mixture consisting of 75 parts by weight of α-methylstyrene and 10 parts by weight of acrylonitrile was added and polymerized for 2 hours. Continuous addition was made over time. Next, 3 parts by weight of α-methylstyrene and 12 parts by weight of acrylonitrile were added over 2 hours while adjusting the concentration of unreacted acrylonitrile in the polymerization system. The concentration of unreacted acrylonitrile in the polymerization system at the end of monomer addition was 35% by weight. After the monomer addition was completed, polymerization was continued for an additional 2 hours. The results after completion of polymerization were as follows. Unreacted α-methylstyrene*1: 0.59% by weight Unreacted acrylonitrile*1: 0.19% by weight Amount of aggregates in copolymer latex: 0.002% by weight Average particle diameter of copolymer latex*2: 0.08μ Softening point *3: 135℃ Thermal decomposition temperature at 50% weight loss: 379℃ - Copolymer (A-2) - 200 parts by weight of deionized water in a reactor purged with nitrogen,
3 parts by weight of sodium lauryl sulfate, 0.7 parts by weight of potassium persulfate, and 0.1 part by weight of n-dodecylmercaptan.
After adding parts by weight, further add α-methylstyrene.
Add 20% by weight of a monomer mixture consisting of 71 parts by weight and 20 parts by weight of acrylonitrile, heat to 70°C and polymerize for 1 hour, then add the remainder of the monomer mixture (80% by weight) continuously for 4 hours. added. Next, 2 parts by weight of α-methylstyrene and 7 parts by weight of acrylonitrile were added over 2 hours while adjusting the concentration of unreacted acrylonitrile in the polymerization system. The concentration of unreacted acrylonitrile in the polymerization system at the end of monomer addition was 43% by weight. After the monomer addition was completed, polymerization was continued for an additional 2 hours. The results after completion of polymerization were as follows. Unreacted α-methylstyrene: 0.29% by weight Unreacted acrylonitrile: 0.16% by weight Amount of aggregates in copolymer latex: 0.002% by weight Average particle diameter of copolymer latex: 0.050μ Softening point of copolymer: 129℃ 50 Thermal decomposition temperature at % weight loss: 392°C - Copolymer (A-3) - 200 parts by weight of deionized water in a reactor purged with nitrogen,
3 parts by weight of sodium lauryl sulfate, 0.7 parts by weight of potassium persulfate, and 0.1 part by weight of n-dodecylmercaptan.
After adding parts by weight and heating to 70°C, 20% of a monomer mixture consisting of 78 parts by weight of α-methylstyrene and 22 parts by weight of acrylonitrile was added, and after polymerizing for 1 hour, the remaining 80% was polymerized for 4 hours. It was added continuously over the period of time. The concentration of unreacted acrylonitrile in the polymerization system at the end of monomer addition was 18% by weight. After the monomer addition was completed, polymerization was continued for an additional 2 hours. The results after completion of polymerization were as follows. Unreacted α-methylstyrene: 7.8% by weight Unreacted acrylonitrile: 0.06% by weight Amount of aggregates in copolymer latex: 0.09% by weight Average particle size in copolymer latex: 0.08μ Softening point of copolymer: 102℃ Thermal decomposition temperature at 50% weight loss: 360°C - Copolymer (A-4) - 120 parts by weight of deionized water in a reactor purged with nitrogen,
2.0 parts by weight of sodium lauryl sulfate, 0.7 parts by weight of potassium persulfate, and n-dodecyl mercaptan
After adding 0.1 part by weight, 20% by weight of a monomer mixture consisting of 75 parts by weight of α-methylstyrene and 10 parts by weight of acrylonitrile was added, heated to 70°C, and polymerized for 1 hour. The remainder of the mass mixture (80% by weight) was added continuously over a period of 4 hours. Next, 3 parts by weight of α-methylstyrene and 12 parts by weight of acrylonitrile were continuously added over 2 hours while adjusting the concentration of unreacted acrylonitrile in the polymerization system. The concentration of unreacted acrylonitrile in the polymerization system after addition was 32% by weight. After the monomer addition was completed, polymerization was continued for an additional 2 hours. The results after completion of polymerization were as follows. . Unreacted α-methylstyrene: 0.77% by weight Unreacted acrylonitrile: 0.23% by weight Amount of aggregates in copolymer latex: 0.42% by weight Average particle size in copolymer latex: 0.13μ Softening point of copolymer: 134°C Thermal decomposition temperature at 50% weight loss: 345°C - Graft polymer (B-1) - In a reactor purged with nitrogen, 60 parts by weight of polybutadiene latex (solid content), 200 parts by weight of deionized water, and ethylenediaminetetraacetic acid diacetate were added. 0.1 part by weight of sodium salt,
Add 0.001 parts by weight of ferric sulfate and 0.4 parts by weight of sodium formaldehyde sulfoxylate at 60°C.
After heating to 13 parts by weight of acrylonitrile, 27 parts by weight of styrene
Parts by weight and Kiyumen hydroperoxide
A mixture consisting of 0.2 parts by weight was continuously added over 3 hours, and polymerization was further carried out at 60°C for 2 hours. -Graft polymer (B-2)- Except that 60 parts by weight of polybutadiene latex was changed to 30 parts by weight, 13 parts by weight of acrylonitrile was changed to 20 parts by weight, and 27 parts by weight of styrene was changed to 50 parts by weight.
It was polymerized in the same manner as graft polymer B-1.
【表】【table】
【表】
実施例２および比較例２
前述の共重合体（Ａ−１〜−４）、グラフト重
合体（Ｂ−１〜−２）および下記構造式を有する
市販のポリカーボネートを表−３に示す割合にて
混練し（バンバリーミキサー、260℃、４分間）、
樹脂組成物を得た。樹脂組成物の物性を表−４に
示す。
[Table] Example 2 and Comparative Example 2 The aforementioned copolymers (A-1 to -4), graft polymers (B-1 to -2), and commercially available polycarbonates having the following structural formulas are shown in Table-3. Knead in proportion (Banbury mixer, 260℃, 4 minutes),
A resin composition was obtained. Table 4 shows the physical properties of the resin composition.
【表】【table】
【表】【table】
【表】【table】
Claims (1)
飽和ニトリル30〜20重量％とをラジカル性開始
剤の存在下、乳化重合する際、両単量体全量添
加終了時における重合系内の全未反応単量体に
対する未反応不飽和ニトリルの濃度が31重量％
以上になるように調整して単量体を添加し、か
つ、共重合体ラテツクス粒子の90％以上が0.1μ
以下となるように重合して得られた共重合体20
〜80重量％および、 (B) ゴム質重合体、芳香族ビニル、不飽和ニトリ
ルおよび／または不飽和カルボン酸エステルよ
りなるグラフト重合体20〜80重量％からなる耐
熱性耐衝撃性樹脂組成物。 ２ 共重合体の熱分解温度（50重量％損失）が
370℃以上である特許請求の範囲第１項記載の耐
熱性耐衝撃性樹脂組成物。 ３ (A) α−アルキルスチレン70〜80重量％と不
飽和ニトリル30〜20重量％とをラジカル性開始
剤の存在下、乳化重合する際、両単量体全量添
加終了時における重合系内の全未反応単量体に
対する未反応不飽和ニトリルの濃度が31重量％
以上になるように調整して単量体を添加し、か
つ、共重合体ラテツクス粒子の90％以上が0.1μ
以下となるように重合して得られた共重合体10
〜50重量％、 (B) ゴム質重合体、芳香族ビニル、不飽和ニトリ
ルおよび／または不飽和カルボン酸エステルよ
りなるグラフト重合体10〜50重量％、 (C) ポリカーボネート30〜60重量％からなる耐熱
性耐衝撃性樹脂組成物。 ４ 共重合体の熱分解温度（50重量％損失）が
370℃以上である特許請求の範囲第３項記載の耐
熱性耐衝撃性樹脂組成物。[Claims] 1 (A) When emulsion polymerizing 70 to 80% by weight of α-alkylstyrene and 30 to 20% by weight of unsaturated nitrile in the presence of a radical initiator, complete addition of both monomers is completed. When the concentration of unreacted unsaturated nitrile is 31% by weight based on the total unreacted monomer in the polymerization system
The monomer is added so that the copolymer latex particles are 0.1μ or more, and 90% or more of the copolymer latex particles are 0.1μ
Copolymer 20 obtained by polymerizing as follows
80% by weight of a heat-resistant impact-resistant resin composition, and (B) 20-80% by weight of a graft polymer made of a rubbery polymer, an aromatic vinyl, an unsaturated nitrile, and/or an unsaturated carboxylic acid ester. 2 The thermal decomposition temperature (50% loss by weight) of the copolymer is
The heat-resistant and impact-resistant resin composition according to claim 1, which has a temperature of 370°C or higher. 3 (A) When emulsion polymerizing 70 to 80% by weight of α-alkylstyrene and 30 to 20% by weight of unsaturated nitrile in the presence of a radical initiator, the amount of Concentration of unreacted unsaturated nitrile based on total unreacted monomer is 31% by weight
The monomer is added in such a way that 90% or more of the copolymer latex particles are 0.1 μm.
Copolymer 10 obtained by polymerizing as follows
-50% by weight, (B) 10-50% by weight of a graft polymer made of a rubbery polymer, aromatic vinyl, unsaturated nitrile and/or unsaturated carboxylic acid ester, (C) 30-60% by weight of polycarbonate Heat-resistant impact-resistant resin composition. 4 The thermal decomposition temperature (50% loss by weight) of the copolymer is
The heat-resistant and impact-resistant resin composition according to claim 3, which has a temperature of 370°C or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19026582A JPS5980455A (en) | 1982-10-28 | 1982-10-28 | Heat-resistant, impact-resistant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19026582A JPS5980455A (en) | 1982-10-28 | 1982-10-28 | Heat-resistant, impact-resistant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5980455A JPS5980455A (en) | 1984-05-09 |
| JPS6365105B2 true JPS6365105B2 (en) | 1988-12-14 |
Family
ID=16255263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19026582A Granted JPS5980455A (en) | 1982-10-28 | 1982-10-28 | Heat-resistant, impact-resistant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5980455A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0621210B2 (en) * | 1984-12-28 | 1994-03-23 | 三菱レイヨン株式会社 | Thermoplastic resin composition |
| JPS62141049A (en) * | 1985-12-13 | 1987-06-24 | Sumitomo Naugatuck Co Ltd | Weather-resistant resin composition having excellent rib strength |
-
1982
- 1982-10-28 JP JP19026582A patent/JPS5980455A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5980455A (en) | 1984-05-09 |
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