JPH0480049B2 - - Google Patents
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- Publication number
- JPH0480049B2 JPH0480049B2 JP59264633A JP26463384A JPH0480049B2 JP H0480049 B2 JPH0480049 B2 JP H0480049B2 JP 59264633 A JP59264633 A JP 59264633A JP 26463384 A JP26463384 A JP 26463384A JP H0480049 B2 JPH0480049 B2 JP H0480049B2
- Authority
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- Japan
- Prior art keywords
- weight
- molecular weight
- styrene
- resin composition
- present
- 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.)
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Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 67
- 239000011342 resin composition Substances 0.000 claims description 37
- 229920005990 polystyrene resin Polymers 0.000 claims description 30
- 229920002857 polybutadiene Polymers 0.000 claims description 29
- 229920001971 elastomer Polymers 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- 239000005060 rubber Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000005227 gel permeation chromatography Methods 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000012745 toughening agent Substances 0.000 description 11
- 238000012662 bulk polymerization Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 9
- 229920005669 high impact polystyrene Polymers 0.000 description 8
- 239000004797 high-impact polystyrene Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 239000005064 Low cis polybutadiene Substances 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-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
- 238000012935 Averaging Methods 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- PBGVMIDTGGTBFS-UHFFFAOYSA-N but-3-enylbenzene Chemical compound C=CCCC1=CC=CC=C1 PBGVMIDTGGTBFS-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
〔産業上の利用分野〕
本発明は、耐衝撃性と引張強度とのバランスに
優れる、ポリスチレン系樹脂組成物およびその製
造法に関する。
〔従来の技術〕
硬質で脆いポリスチレン系樹脂の耐衝撃性を改
良するために各種未加硫ゴムを強靱化剤として用
いることは従来より良く知られ、特に未加硫ゴム
の存在下にスチレン系単量体等を塊状重合または
塊状懸濁重合して得られる耐衝撃性ポリスチレン
系樹脂組成物は安価で加工性および各種物性に優
れ各種用途に広く使用されてきた。この目的に使
用される未加硫ゴムとしてはポリブタジエンゴム
とスチレン−ブタジエン共重合ゴムが一般的であ
り、特に低温における耐衝撃性を必要とする場合
には、各種のポリブタジエンゴム、例えば有機リ
チウム単独又はこれを主成分とするアニオン重合
によつて得られるいわゆるローシスポリブタジエ
ンゴム、またはコバルト、ニツケル、チタン等の
遷移金属化合物を主成分とする配位アニオン触媒
によつて得られるハイシスポリブタジエンゴムが
好ましく、用途、目的に合わせて強靱化剤として
広く用いられてきた。
〔発明が解決しようとする問題点〕
しかしながら、最近の耐衝撃性ポリスチレン系
樹脂に対する要求は、従来以上に高度なものとな
り、例えば耐衝撃性を損なうことなく、光沢或い
は強度の向上を計るといつた、従来、逆相関の関
係にあつて、そのバランスを改良することが困難
であつた特性の改善が求められている。
〔問題点を解決するための手段及び作用〕
これらの要求のなかで、本発明者らは耐衝撃性
と引張強度のバランスを改良するために努め、ア
ニオン重合によつて得られるローシスポリブタジ
エンゴムが、ある特定された構造であるとき、こ
れを限定された重量で、かつ限定された形状で含
有するポリスチレン系樹脂組成物が、上述の要
求、即ち優れた耐衝撃性と引張強度のバランスを
有するものであることを見出した。
即ち、本発明は、
ａ ゲルパーミエーシヨンクロマトグラフで測定
される重量平均分子量が20〜65万、重量平均分
子量と数平均分子量との比で表示される分子量
分布が1.5〜3.0、
ｂ Ｌロータを使用し、100℃で測定されるムー
ニー粘度が60〜100、
ｃ 25℃における５重量％スチレン溶液粘度
〔SV〕が200〜500センチポイズ
のポリブタジエンゴムを２〜20重量％強靱化剤と
して使用してなり、固有粘度〔η〕が0.6〜1.5
dl／ｇであつて、次式(1)に関係を満たし、更に樹
脂中のゴム粒子径が１〜５ミクロンであることを
特徴とする耐衝撃性に優れるポリスチレン系樹脂
組成物およびその製造法である。
400≦SV＋250η≦750 ……(1)
この耐衝撃性ポリスチレン系樹脂組成物は本発
明で規定されるポリブタジエンゴムを２〜20重量
％とスチレン系単量体またはスチレン系単量体と
共重合可能な不飽和化合物との混合物98〜80重量
％を塊状重合、塊状懸濁併用重合または溶液重合
によりラジカル重合させる方法によつて得られ、
得られた樹脂組成物は極めて高度な性能、すなわ
ち耐衝撃性と引張強度との高度のバランスに優れ
る。
本発明で強靱化剤として使用されるポリブタジ
エンゴムは、ゲルパーミエーシヨンクロマトグラ
フ（GPC）で測定される重量平均分子量（ｗ）
が20〜65万、ｗと数平均分子量（ｎ）との比
で表示される分子量分布（ｗ／ｎ）が1.5〜
3.0であることを必要とする。ｗが10万より小
さい場合、本発明で規定される固有粘度と、ゴム
粒子径を有するポリスチレン系樹脂組成物を得る
ことは困難であり、またｗ／ｎが3.0より大
きい場合には、強靱化剤としての効果が不充分で
あつて、本発明の目的とする耐衝撃性と引張強度
とのバランスに優れたポリスチレン系樹脂組成物
を得ることはできない。またｗが80万を越える
場合、又はｗ／ｎが1.5より小さい場合は、
ゴム自体の加工性が不充分であるばかりでなく、
ゴムのスチレン溶液の取扱いも困難である。
ｗ／ｎは、1.8〜2.5であることが好ましい。
又、本発明に用いるポリブタジエンゴムのＬロ
ーターを使用し、100℃で測定されるムーニー粘
度（ML）は60〜100であることを必要とする。
MLが100を超える場合には、加工性等の点でゴ
ムとしての取扱いが困難である。一方、MLが60
未満の場合には、本発明の目的とする、優れた耐
衝撃性と引張強度との物性バランスを達成するこ
とが困難である。好ましいMLは、65〜85であ
る。
更に、本発明に用いるポリブタジエンゴムは25
℃における５重量％スチレン溶液の溶液粘度
（SV）が、200〜500センチポイズであることを必
要とする。200センチポイズ未満の溶液粘度では、
本発明に規定されるポリスチレン系樹脂組成物中
に含まれるゴムの粒子径を形成することが困難と
なり、強靱化剤としての効果が不充分で、耐衝撃
性の点で劣つたものとなる。又、500センチポイ
ズを超えるSVでは、該ポリスチレン系樹脂組成
物の生産にあたつて、スチレンへの溶解性が低下
し、その生産性を悪化させて好ましくない。とく
に好ましい溶液粘度は、250〜350センチポイズで
ある。
本発明の耐衝撃性ポリスチレン系樹脂組成物は
上述したポリブタジエンゴムを２〜20重量％、好
ましくは３〜12重量％含有するポリスチレン系樹
脂組成物である。２重量％未満の使用量では本発
明が目的とする耐衝撃性の改良効果が不十分であ
り、また、20重量％を超える使用では耐衝撃性は
向上するものの本来のポリスチレン系樹脂組成物
の持つ特性、例えば引張強度・剛性を失わせるも
のとなり好ましくない。又、本発明においては、
本発明に用いるポリブタジエンゴム以外に強靱化
剤として少量、例えば１〜10重量％含むものであ
つても良い。この場合、本発明の効果の発現のた
めには、使用する強靱化剤の少なくとも30％は本
発明に用いるポリブタジエンゴムであることを必
要とする。本発明の耐衝撃性ポリスチレン系樹脂
組成物を得る好適な方法は本発明に用いるポリブ
タジエンゴムを２〜20重量パーセントとスチレン
系単量体又はスチレン系単量体と共重合可能な不
飽和化合物との混合物98〜80重量パーセントを塊
状重合、塊状懸濁併用重合または溶液重合により
ラジカル重合させることによる方法である。
本発明で用いられるスチレン系単量体として
は、スチレン、α−メチルスチレン、ビニルトル
エン例えばパラメチルスチレン、ビニルエチルベ
ンゼン、ビニルキシレン、ビニルナフタレン等が
例として挙げられ、１種又は２種以上の混合物と
して用いられる。又、スチレン系単量体と共重合
可能な不飽和化合物としてはアクリロノトリル、
メタクリル酸メチルなとが挙げられる。本発明で
特に好ましいスチレン系単量体はスチレンであ
り、この単独使用ないしはこれと他の単量体の混
合物であつて混合物中のスチレンの比率が50重量
パーセント以上の場合である。
本発明の耐衝撃性ポリスチレン系樹脂組成物を
得る好ましい方法の一つである塊状重合は一般に
次のように実施される。まず本発明で特定された
ポリブタジエンゴムをスチレンに溶解し、ラジカ
ル開始剤を用いない無触媒の場合は50〜250℃の
重合温度において加熱重合する。またラジカル開
始剤を触媒として用いる場合には、ラジカル開始
剤の分解温度に合わせて20〜200℃において重合
し、スチレンの反応率が所望のものとなるまで重
合操作が継続される。この塊状重合に際しては、
しばしば連鎖移動剤の1000〜5000ppmが添加され
る。重合終了後、生成ポリマー中に少量、通常は
30重量パーセント以下の未反応スチレンを含有す
る場合は、かかるスチレンを公知の方法、たとえ
ば加熱下での減圧除去あるいは揮発分除去の目的
に設計された押出装置で除去するなどの方法によ
つて除去することが望ましい。かかる塊状重合中
の攪拌は、必要に応じて行なわれるが、スチレン
の重合体への転化率、すなわちスチレンの重合率
が30％以上にまで進んだあとは、攪拌は停止する
か緩和するのが望ましい。過度の攪拌は得られる
重合体の強度を低下させることがある。また必要
なら少量のトルエン、エチルベンゼン等の希釈溶
剤の存在下で重合し、重合終了後に未反応スチレ
ンとともにこれら希釈溶剤を加熱除去しても良
い。
また、塊状懸濁併用重合も本発明の耐衝撃性ポ
リスチレン系樹脂組成物の製造に有用である。こ
の方法はまず前半の反応を塊状で行ない後半の反
応を懸濁状態で行なうものである。すなわち本発
明に用いる特定のポリブタジエンゴムのスチレン
溶液を、先の塊状重合の場合と同様に無触媒下で
加熱重合又は触媒添加重合し、あるいは照射重合
して、スチレンの通常50％以下、特に好ましくは
10ないし40％までを部分的に重合させる。これが
前半の塊状重合である。ついでこの部分的に重合
した混合物を懸濁安定剤またはこれと界面活性剤
の両者の存在下に水性媒体中に攪拌下に分散さ
せ、反応の後半を懸濁重合で完結させ、先の塊状
重合の場合と同様に、洗浄、乾燥し、必要により
ペレツトまたは粉末化し、実用に供するものであ
る。
本発明の、こうして得られた耐衝撃性ポリスチ
レン系樹脂組成物はスチレン系重合体の硬い相と
軟質成分、すなわちスチレン等とグラフト共重合
したポリブタジエンゴムおよびこれに封じ込めら
れたスチレン系重合体の分散粒子からなつてい
る。
一般的にいつて、耐衝撃性ポリスチレン系樹脂
組成物中のこの硬いスチレン系重合体相の固有粘
度が、大きくなる程、樹脂組成の強度は向上する
が、大きすぎる場合、加工性の点で好ましくな
い。一方、軟質成分である強靱化剤としてのポリ
ブタジエンゴムの粒子径は、ある程度大きいもの
であることが、該樹脂の耐衝撃性の向上に必要で
ある。しかし、この場合逆に引張強度は低下し、
更にゴム粒子径があまりにも大きすぎる場合に
は、耐衝撃性も低下する。
本発明の耐衝撃性ポリスチレン系樹脂組成物
は、ある特定されたゴム粒子径と、固有粘度を有
する場合、耐衝撃性と引張強度或いは伸び等の物
性バランスの点で、非常に優れた特性を発揮す
る。
即ち、本発明の耐衝撃性ポリスチレン系樹脂組
成物はゴム粒子径が、その平均値で表示した、１
〜５ミクロンであることを必要とする。
ここで、平均粒子径とは、樹脂の超薄切片法に
よる電子顕微鏡写真を撮影し、写真中の軟質成分
粒子200〜500個の粒子径を測定し、次式により重
量平均したものである。
重量平均径＝ΣnD4／ΣnD3
ここで、ｎは粒子径Ｄの軟質成分粒子の個数で
ある。
ゴム粒子径が１ミクロン未満である場合は、該
ポリスチレン系樹脂組成物の耐衝撃性は不充分で
あり、また５ミクロンを超える場合には強度や剛
性が不充分となる。更に大きすぎる場合、耐衝撃
性も低下して好ましくない、特に好ましいゴム粒
子径は、平均値で示して、1.5〜３ミクロンであ
る。
更に、該耐衝撃性ポリスチレン系樹脂組成物の
25℃、トルエン中で測定される固有粘度〔η〕は
0.6〜1.5dl／ｇであることが必要であつて、しか
も先述した25℃でのポリブタジエンゴムの５重量
％スチレン溶液粘度〔SV〕との間に次の関係式
(1)が成立することも必要とする。
400≦SV＋250η≦750 ……(1)
固有粘度が0.6dl／ｇ未満である場合、該ポリ
スチレン系樹脂組成物の強度は不充分なものとな
り、固有粘度が1.5dl／ｇを超える場合には、そ
の加工性が劣つて好ましくない。更に、本発明の
目的とする、耐衝撃性と強度との関係において、
より高度なバランスを有するポリスチレン系樹脂
組成物を得るには、上式(1)が成立することが必要
であつて、その値が400未満である場合、得られ
る硬いポリスチレン系重合体相とのバランスにお
いて、ゴム粒子径は小さいものであり、従つて耐
衝撃性の点で劣るものとなる。一方、その値が
750を超える場合、耐衝撃性の点ではある程度好
ましいものの、強度の点で劣つたものとなり、更
には、光沢等外観性においても優れた物性バラン
スを有するものは得られない。
本発明で規定される耐衝撃性ポリスチレン系樹
脂組成物の特に好ましい固有粘度は0.8〜1.0dl／
ｇであり、更に該ポリスチレン系樹脂組成物の固
有粘度〔η〕と、強靱化剤ゴムの５重量％スチレ
ン溶液粘度〔SV〕との上記関係式(1)の特に好ま
しい値の範囲は、500〜600である。
上述のような規定されたゴム粒子径と、固有粘
度とを有するポリスチレン系樹脂組成物を得る為
に、本発明の特定された構造を有するポリブタジ
エンゴムの使用は、好適である。
〔効果〕
本発明の耐衝撃性ポリスチレン系樹脂組成物
は、従来のスチレン、或いはスチレンを主成分と
する耐衝撃性ポリスチレン系樹脂組成物に比べ、
極めて優れた耐衝撃性を有するのみでなく、これ
と、引張強度、伸び等の物性バランスにおいて、
従来の樹脂組成物に比較してはるかに優れ、また
外観も優秀である。しかも設備の改造等を行うこ
となく生産性も充分であり、本発明の工業的意義
は極めて大きい。
本発明の耐衝撃性ポリスチレン系樹脂組成物
は、射出成形、押出成形等の加工法で多種多様に
実用上有用な製品として使用できるが、特に低温
で用いられる射出成形品、又はシート、フイル
ム、特に油性食品包装用途に好適である。更に加
工に際し、必要に応じて、難燃化剤、酸化防止
剤、紫外線吸収剤、滑剤、離形剤、充填剤等、更
に他の熱可塑性樹脂例えば一般用ポリスチレン、
メタクリル樹脂等と混合して用いても良い。本発
明の効果はとくに難燃化剤を添加しての難燃性与
時に大きく発揮される。
〔実施例〕
以下、若干の実施例により、本発明の具体的実
施態様を示すが、これは本発明の趣旨をより具体
的に説明するためのものであつて、本発明を限定
するものではない。
実施例１，２及び比較例１〜５
第１表に示すポリブタジエンゴムＡ〜Ｄは、ブ
チルリチウムを触媒とする溶液重合法によつて得
たものであり、Ｅ〜Ｇは遷移金属触媒を用いて得
たポリブタジエンゴムである。これらのゴムを強
靱化剤として使用し、以下の方法で塊状重合を行
なつた。
ポリブタジエンゴム８重量部をスチレン92重量
部とエチルベンゼン８重量部に溶解し、更にスチ
レンに対して0.05重量部のベンゾイルパーオキシ
ドと0.10重量部のα−メチルスチレン２重量体を
添加し、80℃で４時間、110℃で４時間、150℃で
４時間、攪拌下に重合を行なつた。更に230℃前
後で30分間加熱処理を行ない、その後、未反応ス
チレン及びエチルベンゼンの真空除去を行なつて
ポリスチレン系樹脂組成物を得た。これを粉砕
後、押出機でペレツト状とし、射出成形して物性
を測定した。その結果を第２表に示す。
実施例 ３
ポリブタジエンゴムＡとスチレンの重量のみを
各々12重量部、88重量部に変える以外は実施例１
と同様に実施した。得られた結果を第２表に示
す。
実施例 ４
塊状懸濁併用重合によつて耐衝撃性ポリスチレ
ン系樹脂を得た。ポリブタジエンゴムＢの６重量
部をスチレン94重量部に溶解し、攪拌下にスチレ
ン重合率が約30％になるまで約５時間重合を行な
い、これを第３リン酸カルシウム３重量部、ドデ
シルベンゼンスルホン酸ナトリウム0.02重量部を
含む水150重量部に懸濁させ、この懸濁液にベン
ゾイルパーオキサイド0.3重量部、ジターシヤリ
ーブチルパーオキサイド0.05重量部を添加し、80
℃で２時間、110℃で２時間、更に130℃で２時間
重合させ重合を完結した。得られた懸濁粒子は
別、乾燥し押出機にてペレツトとして射出成形し
て物性を測定した。結果を第２表に示す。
[Industrial Application Field] The present invention relates to a polystyrene-based resin composition that has an excellent balance between impact resistance and tensile strength, and a method for producing the same. [Prior Art] It has been well known that various unvulcanized rubbers are used as toughening agents to improve the impact resistance of hard and brittle polystyrene resins. Impact-resistant polystyrene resin compositions obtained by bulk polymerization or bulk suspension polymerization of monomers, etc. are inexpensive and have excellent processability and various physical properties, and have been widely used for various purposes. Polybutadiene rubber and styrene-butadiene copolymer rubber are commonly used as unvulcanized rubbers for this purpose.In particular, when impact resistance at low temperatures is required, various polybutadiene rubbers, such as organolithium alone Or so-called low-cis polybutadiene rubber obtained by anionic polymerization containing this as a main component, or high-cis polybutadiene rubber obtained by a coordination anion catalyst containing a transition metal compound such as cobalt, nickel, or titanium as a main component. It is preferred and has been widely used as a toughening agent depending on the application and purpose. [Problems to be Solved by the Invention] However, recent demands for impact-resistant polystyrene resins have become more sophisticated than before. In addition, there is a need to improve the characteristics, which have conventionally been inversely correlated and it has been difficult to improve the balance. [Means and effects for solving the problems] In response to these demands, the present inventors have endeavored to improve the balance between impact resistance and tensile strength, and have developed a low-cis polybutadiene rubber obtained by anionic polymerization. has a certain specific structure, a polystyrene resin composition containing it in a limited weight and in a limited shape can meet the above requirements, that is, an excellent balance between impact resistance and tensile strength. I found out that it has something to do with it. That is, the present invention provides: a) a weight average molecular weight measured by gel permeation chromatography of 200,000 to 650,000; a molecular weight distribution expressed as the ratio of weight average molecular weight to number average molecular weight of 1.5 to 3.0; and b) an L rotor. 2 to 20% by weight of polybutadiene rubber with a Mooney viscosity measured at 100°C of 60 to 100 and a 5% by weight styrene solution viscosity [SV] of 200 to 500 centipoise at 25°C as a toughening agent. and the intrinsic viscosity [η] is 0.6 to 1.5.
dl/g, satisfies the following formula (1), and has a rubber particle size in the resin of 1 to 5 microns, and a polystyrene resin composition with excellent impact resistance, and a method for producing the same. It is. 400≦SV+250η≦750 (1) This impact-resistant polystyrene resin composition can be copolymerized with 2 to 20% by weight of the polybutadiene rubber specified in the present invention and a styrene monomer or a styrene monomer. obtained by radical polymerization of 98 to 80% by weight of a mixture with an unsaturated compound by bulk polymerization, combined bulk suspension polymerization, or solution polymerization,
The resulting resin composition has extremely high performance, that is, it has excellent balance between impact resistance and tensile strength. The polybutadiene rubber used as a toughening agent in the present invention has a weight average molecular weight (w) measured by gel permeation chromatography (GPC).
is 200,000 to 650,000, and the molecular weight distribution (w/n) expressed as the ratio of w to number average molecular weight (n) is 1.5 to 650,000.
Requires 3.0. When w is less than 100,000, it is difficult to obtain a polystyrene resin composition that has the inherent viscosity and rubber particle size specified in the present invention, and when w/n is greater than 3.0, toughening is difficult. The effect as an agent is insufficient, and it is impossible to obtain a polystyrene resin composition with an excellent balance between impact resistance and tensile strength, which is the object of the present invention. Also, if w exceeds 800,000 or w/n is less than 1.5,
Not only is the processability of the rubber itself insufficient;
Handling styrene solutions of rubber is also difficult.
It is preferable that w/n is 1.8 to 2.5. Further, the Mooney viscosity (ML) of the polybutadiene rubber used in the present invention, measured at 100° C. using an L rotor, is required to be 60 to 100.
If the ML exceeds 100, it is difficult to handle it as a rubber in terms of processability, etc. On the other hand, ML is 60
If it is less than that, it is difficult to achieve the excellent physical property balance between impact resistance and tensile strength, which is the objective of the present invention. A preferred ML is 65-85. Furthermore, the polybutadiene rubber used in the present invention is 25
The solution viscosity (SV) of the 5% by weight styrene solution at °C is required to be between 200 and 500 centipoise. For solution viscosities below 200 centipoise,
It becomes difficult to form the particle size of the rubber contained in the polystyrene resin composition defined in the present invention, resulting in insufficient effect as a toughening agent and poor impact resistance. In addition, an SV exceeding 500 centipoise is undesirable since the solubility in styrene decreases and the productivity deteriorates when producing the polystyrene resin composition. A particularly preferred solution viscosity is between 250 and 350 centipoise. The impact-resistant polystyrene resin composition of the present invention is a polystyrene resin composition containing 2 to 20% by weight, preferably 3 to 12% by weight of the above-mentioned polybutadiene rubber. If the amount used is less than 2% by weight, the impact resistance improvement effect aimed at by the present invention will be insufficient, and if the amount used exceeds 20% by weight, although the impact resistance will be improved, the original polystyrene resin composition will not be improved. This is undesirable because it causes a loss of properties such as tensile strength and rigidity. Moreover, in the present invention,
In addition to the polybutadiene rubber used in the present invention, a small amount, for example 1 to 10% by weight, of a toughening agent may be included. In this case, in order to achieve the effects of the present invention, at least 30% of the toughening agent used must be the polybutadiene rubber used in the present invention. A preferred method for obtaining the impact-resistant polystyrene resin composition of the present invention is to mix 2 to 20 weight percent of the polybutadiene rubber used in the present invention with a styrenic monomer or an unsaturated compound copolymerizable with the styrenic monomer. This method involves radically polymerizing 98 to 80 percent by weight of a mixture of the following by bulk polymerization, combined bulk suspension polymerization, or solution polymerization. Examples of the styrenic monomer used in the present invention include styrene, α-methylstyrene, vinyltoluene, paramethylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, etc. One type or a mixture of two or more types can be mentioned. used as. In addition, examples of unsaturated compounds copolymerizable with styrenic monomers include acrylonotrile,
Examples include methyl methacrylate. A particularly preferred styrene monomer in the present invention is styrene, which is used alone or in a mixture with other monomers, and the proportion of styrene in the mixture is 50% by weight or more. Bulk polymerization, which is one of the preferred methods for obtaining the high impact polystyrene resin composition of the present invention, is generally carried out as follows. First, the polybutadiene rubber specified in the present invention is dissolved in styrene and polymerized by heating at a polymerization temperature of 50 to 250° C. in the case of no catalyst without using a radical initiator. When a radical initiator is used as a catalyst, polymerization is carried out at a temperature of 20 to 200° C. in accordance with the decomposition temperature of the radical initiator, and the polymerization operation is continued until the reaction rate of styrene reaches a desired level. During this bulk polymerization,
Often 1000-5000 ppm of chain transfer agent is added. After the polymerization is complete, a small amount, usually
If it contains less than 30 percent by weight of unreacted styrene, such styrene is removed by known methods, such as removal under reduced pressure under heat or in extrusion equipment designed for the purpose of removing volatiles. It is desirable to do so. Stirring during such bulk polymerization is performed as necessary, but after the conversion rate of styrene to a polymer, that is, the polymerization rate of styrene has reached 30% or more, it is recommended to stop or reduce the stirring. desirable. Excessive stirring may reduce the strength of the resulting polymer. If necessary, the polymerization may be carried out in the presence of a small amount of a diluting solvent such as toluene or ethylbenzene, and after the completion of the polymerization, these diluting solvents may be removed together with unreacted styrene by heating. Bulk suspension combined polymerization is also useful in producing the high impact polystyrene resin composition of the present invention. In this method, the first half of the reaction is carried out in bulk, and the second half is carried out in suspension. That is, a styrene solution of the specific polybutadiene rubber used in the present invention is subjected to heat polymerization or catalyst addition polymerization in the same manner as in the previous bulk polymerization, or to irradiation polymerization to obtain a styrene solution that is usually 50% or less of styrene, particularly preferably. teeth
Partially polymerize up to 10 to 40%. This is the first half of bulk polymerization. This partially polymerized mixture is then dispersed under stirring in an aqueous medium in the presence of a suspension stabilizer or both thereof and a surfactant, and the second half of the reaction is completed by suspension polymerization, and the previous bulk polymerization is completed. In the same way as in the case of 1., it is washed, dried and, if necessary, made into pellets or powder, and then used for practical use. The thus obtained impact-resistant polystyrene resin composition of the present invention consists of a hard phase of a styrenic polymer and a soft component, that is, a polybutadiene rubber graft-copolymerized with styrene, etc., and a dispersion of a styrenic polymer encapsulated therein. It is made up of particles. Generally speaking, as the intrinsic viscosity of this hard styrene polymer phase in the impact-resistant polystyrene resin composition increases, the strength of the resin composition improves. Undesirable. On the other hand, the particle size of polybutadiene rubber as a toughening agent, which is a soft component, is required to be large to some extent in order to improve the impact resistance of the resin. However, in this case, the tensile strength decreases,
Furthermore, if the rubber particle size is too large, the impact resistance will also decrease. When the impact-resistant polystyrene resin composition of the present invention has a specific rubber particle size and intrinsic viscosity, it exhibits extremely excellent properties in terms of the balance of physical properties such as impact resistance and tensile strength or elongation. Demonstrate. That is, the impact-resistant polystyrene resin composition of the present invention has a rubber particle diameter of 1, expressed as an average value.
~5 microns. Here, the average particle diameter is the one obtained by taking an electron micrograph of the resin using an ultrathin section method, measuring the particle diameters of 200 to 500 soft component particles in the photograph, and averaging them by weight according to the following formula. Weight average diameter=ΣnD 4 /ΣnD 3 where n is the number of soft component particles having particle diameter D. If the rubber particle diameter is less than 1 micron, the impact resistance of the polystyrene resin composition will be insufficient, and if it exceeds 5 microns, the strength and rigidity will be insufficient. Furthermore, if it is too large, the impact resistance will also deteriorate, which is undesirable.A particularly preferred rubber particle diameter is 1.5 to 3 microns, expressed as an average value. Furthermore, the impact-resistant polystyrene resin composition
The intrinsic viscosity [η] measured in toluene at 25℃ is
It is necessary that the value is 0.6 to 1.5 dl/g, and the following relational expression is established between the above-mentioned 5 wt% styrene solution viscosity of polybutadiene rubber at 25°C [SV].
It is also necessary that (1) holds true. 400≦SV+250η≦750...(1) If the intrinsic viscosity is less than 0.6 dl/g, the strength of the polystyrene resin composition will be insufficient, and if the intrinsic viscosity exceeds 1.5 dl/g, It is not preferable because its workability is poor. Furthermore, in the relationship between impact resistance and strength, which is the object of the present invention,
In order to obtain a polystyrene-based resin composition with a higher degree of balance, it is necessary that the above formula (1) holds true, and if the value is less than 400, the resulting hard polystyrene-based polymer phase On balance, the rubber particle size is small, and therefore the impact resistance is poor. On the other hand, if its value is
If it exceeds 750, although it is somewhat preferable in terms of impact resistance, it will be inferior in terms of strength, and furthermore, it will not be possible to obtain a product with an excellent balance of physical properties in terms of appearance such as gloss. A particularly preferable intrinsic viscosity of the impact-resistant polystyrene resin composition defined in the present invention is 0.8 to 1.0 dl/
g, and a particularly preferable value range of the above relational expression (1) between the intrinsic viscosity [η] of the polystyrene resin composition and the 5% by weight styrene solution viscosity [SV] of the toughening agent rubber is 500 g. ~600. In order to obtain a polystyrene resin composition having the defined rubber particle size and intrinsic viscosity as described above, it is suitable to use the polybutadiene rubber having the specified structure of the present invention. [Effects] The impact-resistant polystyrene resin composition of the present invention has a higher impact resistance than conventional styrene or impact-resistant polystyrene resin compositions containing styrene as a main component.
Not only does it have extremely excellent impact resistance, but it also has a balance of physical properties such as tensile strength and elongation.
It is far superior to conventional resin compositions and has an excellent appearance. Moreover, productivity is sufficient without any modification of equipment, and the industrial significance of the present invention is extremely large. The impact-resistant polystyrene resin composition of the present invention can be used as a wide variety of practically useful products by processing methods such as injection molding and extrusion molding, but in particular injection molded products used at low temperatures, sheets, films, etc. It is particularly suitable for packaging oil-based foods. Furthermore, during processing, flame retardants, antioxidants, ultraviolet absorbers, lubricants, mold release agents, fillers, etc., and other thermoplastic resins such as general purpose polystyrene, etc. may be added as necessary.
It may be used in combination with methacrylic resin or the like. The effects of the present invention are particularly great when flame retardant is imparted by adding a flame retardant. [Examples] Hereinafter, specific embodiments of the present invention will be shown by some examples, but these are for explaining the gist of the present invention more specifically, and are not intended to limit the present invention. do not have. Examples 1 and 2 and Comparative Examples 1 to 5 Polybutadiene rubbers A to D shown in Table 1 were obtained by a solution polymerization method using butyllithium as a catalyst, and E to G were obtained using a transition metal catalyst. This is polybutadiene rubber obtained by Using these rubbers as toughening agents, bulk polymerization was carried out in the following manner. 8 parts by weight of polybutadiene rubber was dissolved in 92 parts by weight of styrene and 8 parts by weight of ethylbenzene, and 0.05 parts by weight of benzoyl peroxide and 0.10 parts by weight of α-methylstyrene were added to the styrene, and the mixture was heated at 80°C. Polymerization was carried out under stirring for 4 hours, at 110°C for 4 hours, and at 150°C for 4 hours. Further, heat treatment was performed at around 230° C. for 30 minutes, and then unreacted styrene and ethylbenzene were removed in vacuo to obtain a polystyrene resin composition. After pulverizing this, it was made into pellets using an extruder, injection molded, and the physical properties were measured. The results are shown in Table 2. Example 3 Example 1 except that only the weights of polybutadiene rubber A and styrene were changed to 12 parts by weight and 88 parts by weight, respectively.
It was carried out in the same way. The results obtained are shown in Table 2. Example 4 A high-impact polystyrene resin was obtained by combined bulk suspension polymerization. 6 parts by weight of polybutadiene rubber B was dissolved in 94 parts by weight of styrene and polymerized with stirring for about 5 hours until the styrene polymerization rate reached about 30%. 0.02 parts by weight of water, 0.3 parts by weight of benzoyl peroxide and 0.05 parts by weight of ditertiary butyl peroxide were added to this suspension, and 80 parts by weight of
Polymerization was completed at 110°C for 2 hours, then at 130°C for 2 hours. The obtained suspended particles were separately dried and injection molded into pellets using an extruder, and their physical properties were measured. The results are shown in Table 2.
【表】【table】
【表】【table】
【表】
比較例 ６
実施例１と使用するポリブダジエンゴムも同じ
とし、80℃での攪拌下の重合のみ攪拌数を1/2と
する以外は、実施例１と同様にして実施した。得
られたHIPSの構造と物性を表２に示したがゴム
粒径は5.5μであり、ゴム粒径が本発明の範囲内に
ないHIPSが得られた。このHIPSの強度は215
Kg／cm2であり、実施例に比し劣る。
比較例 ７
実施例２と使用するポリブタジエンゴムも同じ
としてベンゾイルパーオキシドを0.03重量部に減
量して実施する以外は実施例２と同様にして実施
した。得られたHIPSの構造と物性を表２に示し
たが、このものはSV＋250η＝780であり、この値
は本発明の範囲外の値である。このHIPSは衝撃
強度が18.0Kg・cm／cm、強度が210Kg／cm2であり、
両者のバランスが実施例に比し劣る。
すなわち、以上のとおり、本発明の樹脂組成物
中のゴム粒径が５ミクロンを超えると引張または
曲げ強度の低下があり、（比較例６）または、た
とえ、１〜５ミクロンにこれをコントロールして
も得られる組成物中の〔η〕に係る式 SV＋
250ηが400〜750の範囲内にないと衝撃強度と引
張または曲げ強度とのバランスが改良されない。
（比較例７）
上述の〔SV〕と〔η〕との関係とその他の必
須要件に照した各実施例、各比較例の位置づけを
第１図に示した。ここに比較例３は原料のムーニ
ー粘度および〔SV〕が低すぎるものであり、比
較例５はその分子量分布が広すぎるものであり、
比較例６はゴムの粒径が大きすぎるものである。
また、図中Ａ〜Ｇは第１表に示した強靱化剤と
してのポリブタジエンゴムの種類を示す。[Table] Comparative Example 6 The same polybutadiene rubber was used as in Example 1, and the polymerization was carried out in the same manner as in Example 1, except that the number of stirrings was halved only in the polymerization under stirring at 80°C. The structure and physical properties of the obtained HIPS are shown in Table 2, and the rubber particle size was 5.5μ, indicating that HIPS whose rubber particle size was not within the range of the present invention was obtained. The strength of this HIPS is 215
Kg/cm 2 , which is inferior to the example. Comparative Example 7 A test was carried out in the same manner as in Example 2, except that the polybutadiene rubber used was the same as in Example 2, and the amount of benzoyl peroxide was reduced to 0.03 parts by weight. The structure and physical properties of the obtained HIPS are shown in Table 2, and this one has SV+250η=780, which is a value outside the scope of the present invention. This HIPS has an impact strength of 18.0Kg/cm2 and a strength of 210Kg/ cm2 .
The balance between the two is inferior to that of the example. That is, as described above, when the rubber particle size in the resin composition of the present invention exceeds 5 microns, the tensile or bending strength decreases (Comparative Example 6), or even if this is controlled to 1 to 5 microns. The formula related to [η] in the composition obtained by
If 250η is not within the range of 400 to 750, the balance between impact strength and tensile or bending strength will not be improved.
(Comparative Example 7) FIG. 1 shows the positioning of each example and each comparative example in light of the relationship between [SV] and [η] described above and other essential requirements. Here, in Comparative Example 3, the Mooney viscosity and [SV] of the raw material were too low, and in Comparative Example 5, the molecular weight distribution was too wide.
In Comparative Example 6, the rubber particle size was too large. Further, A to G in the figure indicate the types of polybutadiene rubbers as toughening agents shown in Table 1.
第１図は〔SV〕と〔η〕との関係とその他の
必須要件に照した各実施例と各比較例との位置づ
けを示した説明図である。
FIG. 1 is an explanatory diagram showing the relationship between [SV] and [η] and the positioning of each example and each comparative example in light of other essential requirements.
Claims (1)
測定される重量平均分子量が20〜65万、重量平
均分子量と数平均分子量との比で表示される分
子量分布が1.5〜3.0、 ｂ Ｌロータを使用し、100℃で測定されるムー
ニー粘度が60〜100、 ｃ 25℃における５重量％スチレン溶液粘度
〔SV〕が200〜500センチポイズ であるポリブタジエンゴムを２〜20重量％と、ス
チレン系単量体またはこれとスチレン系単量体と
共重合可能な不飽和化合物との混合物98〜80重量
％とを、塊状、塊状懸濁、または溶液状態でラジ
カル重合して得られるポリスチレン系樹脂組成物
であり、得られる樹脂の固有粘度〔η〕が0.6〜
1.5dl／ｇであり、かつ、次式の関係を満たし、
更に、組成物中のゴム粒子径が１〜５ミクロンで
あることを特徴とする耐衝撃性に優れるポリスチ
レン系樹脂組成物 400≦SV＋250η≦750 ２ ａ ゲルパーミエーシヨンクロマトグラフで
測定される重量平均分子量が20〜65万、重量平
均分子量と数平均分子量との比で表示される分
子量分布が1.5〜3.0、 ｂ Ｌロータを使用し、100℃で測定されるムー
ニー粘度が60〜100、 ｃ 25℃における５重量％スチレン溶液粘度
〔SV〕が200〜500センチポイズ であるポリブタジエンゴムを２〜20重量％と、ス
チレン系単量体またはこれとスチレン系単量体と
共重合可能な不飽和化合物との混合物98〜80重量
％とを、塊状、塊状懸濁、または溶液状態でラジ
カル重合することを特徴とする、得られるポリス
チレン系樹脂組成物において、得られる樹脂の固
有粘度〔η〕が0.6〜1.5dl／ｇであり、かつ、次
式の関係を満たし、更に、組成物中のゴム粒子径
が１〜５ミクロンであることを特徴とする耐衝撃
性に優れるポリスチレン系樹脂組成物の製造法。 400≦SV＋250η≦750[Scope of Claims] 1 a Weight average molecular weight measured by gel permeation chromatography is 200,000 to 650,000, molecular weight distribution expressed as the ratio of weight average molecular weight to number average molecular weight is 1.5 to 3.0, b L Using a rotor, the Mooney viscosity measured at 100℃ is 60 to 100, and the 5 weight% styrene solution viscosity [SV] at 25℃ is 200 to 500 centipoise. A polystyrene resin composition obtained by radical polymerization of a monomer or a mixture of the monomer, a styrene monomer, and an unsaturated compound copolymerizable with 98 to 80% by weight in a lump, a lump suspension, or a solution state. The intrinsic viscosity [η] of the resulting resin is 0.6~
1.5dl/g, and satisfies the relationship of the following formula,
Furthermore, a polystyrene-based resin composition with excellent impact resistance characterized in that the rubber particle size in the composition is 1 to 5 microns 400≦SV+250η≦750 2 a Weight average measured by gel permeation chromatography Molecular weight is 200,000 to 650,000, molecular weight distribution expressed as the ratio of weight average molecular weight to number average molecular weight is 1.5 to 3.0, b Mooney viscosity measured at 100°C using an L rotor is 60 to 100, c 25 2 to 20% by weight of polybutadiene rubber having a 5% by weight styrene solution viscosity [SV] of 200 to 500 centipoise at °C, and a styrenic monomer or an unsaturated compound copolymerizable with the styrene monomer. 98 to 80% by weight of a mixture of 1.5 dl/g, satisfies the following relationship, and furthermore, the rubber particle diameter in the composition is 1 to 5 microns. A method for producing a polystyrene resin composition having excellent impact resistance. . 400≦SV＋250η≦750
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26463384A JPS61143414A (en) | 1984-12-17 | 1984-12-17 | Polystyrenic resin and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26463384A JPS61143414A (en) | 1984-12-17 | 1984-12-17 | Polystyrenic resin and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61143414A JPS61143414A (en) | 1986-07-01 |
| JPH0480049B2 true JPH0480049B2 (en) | 1992-12-17 |
Family
ID=17406054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26463384A Granted JPS61143414A (en) | 1984-12-17 | 1984-12-17 | Polystyrenic resin and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61143414A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2659547B2 (en) * | 1987-12-28 | 1997-09-30 | 新日鐵化学株式会社 | Rubber-modified styrenic resin and method for producing the same |
| JP2689124B2 (en) * | 1988-02-22 | 1997-12-10 | 住友化学工業株式会社 | Styrene resin composition |
| JPH0714989B2 (en) * | 1989-03-10 | 1995-02-22 | 新日鐵化学株式会社 | Method for producing rubber-modified styrenic resin |
| JPH0714990B2 (en) * | 1990-03-02 | 1995-02-22 | 新日鐵化学株式会社 | Method for producing rubber-modified styrenic resin |
| KR100217804B1 (en) * | 1990-05-21 | 1999-09-01 | 치어즈 엠. 노우드 | Monovinylaromatic polymer with improved environmental stress crack resistance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51117792A (en) * | 1975-04-10 | 1976-10-16 | Mitsui Toatsu Chem Inc | Preparation of rubber-modified resin with good shock resistance |
| JPS5221094A (en) * | 1975-07-14 | 1977-02-17 | Asahi Chem Ind Co Ltd | Process for producing high-impact polystyrene resins |
-
1984
- 1984-12-17 JP JP26463384A patent/JPS61143414A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51117792A (en) * | 1975-04-10 | 1976-10-16 | Mitsui Toatsu Chem Inc | Preparation of rubber-modified resin with good shock resistance |
| JPS5221094A (en) * | 1975-07-14 | 1977-02-17 | Asahi Chem Ind Co Ltd | Process for producing high-impact polystyrene resins |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61143414A (en) | 1986-07-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |