JP3939036B2 - Novel rubbery polymer composition and impact-resistant styrenic resin composition - Google Patents

Description

但し、ＴＳ＝ＡＳ＋ＢＳ＋ＣＳ
（ＴＳはブロック共重合体（Ｉ）中の芳香族ビニル単量体含量、ＢＳはブロック共重合体（Ｉ）中のブロックとなっている芳香族ビニル単量体含量を表す。）
すなわち、ブロック共重合体（Ｉ）中のブロックとなっていない芳香族ビニル単量体含量（ＴＳ−ＢＳ）の５０重量％以上が、ブロックＡ１（共役ジエン系単量体と芳香族ビニル単量体からなるランダム共重合体）中に含有している必要がある。好ましくは、１．０〜０．７の範囲である。
【００１６】
また、芳香族ビニル−共役ジエン系ランダム共重合体であるブロックＡ１又はブロックＣ中に、ブロック共重合体（Ｉ）に対して５重量％未満の芳香族ビニル単量体ブロックを有していても良い。
ブロック共重合体（Ｉ）中のブロックＡ１における共役ジエン系単量体と芳香族ビニル単量体の重量比は９５：５〜２０：８０の範囲が好ましい。さらに好ましくは７０：３０〜３０：７０の範囲である。また、芳香族ビニル−共役ジエン系ランダム共重合体ブロックＣにおける共役ジエン系単量体と芳香族ビニル単量体の重量比は１００：０〜３０：７０の範囲が好ましい。さらに好ましくは１００：０〜５０：５０の範囲である。
【００１７】
本発明のブロック共重合体（Ｉ）中の全芳香族ビニル単量体含量は５〜６０重量％の範囲である。好ましくは１５〜４５重量％の範囲である。５重量％未満では、ゴム状重合体組成物自体のコールドフローが著しく大きくなり、ゴムの貯蔵、輸送に問題が生じ、ゴムとしての取り扱いが困難となる。また、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、耐衝撃性は向上するものの光沢が若干劣り好ましくない。６０重量％を越えると、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の光沢は良好であるが耐衝撃強度が劣り好ましくない。
【００１８】
次に、本発明のブロック共重合体（Ｉ）中のブロックとなっている芳香族ビニル単量体含量は５〜５０重量％の範囲である。好ましくは１０〜３０重量％の範囲である。ブロックとなっている芳香族ビニル単量体含量が５重量％未満の場合、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の耐衝撃性は向上するものの光沢が若干劣り、光沢の優れるゴム変性耐衝撃性樹脂組成物を得ようとするならば５重量％以上が好ましい。また、５０重量％を越えると、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の光沢は良好であるが耐衝撃強度が劣り好ましくない。更に、ゴム状重合体組成物は粉末状になり易く、しかも成形性が悪くベール状になりにくいという問題が発生して好ましくない。
【００１９】
また、ブロック共重合体（Ｉ）中のブロックとなっている芳香族ビニル重合体のゲルパーミエーションクロマトグラフで測定されるポリスチレン換算の重量平均分子量（Ｍｗ）は５，０００〜１５０，０００の範囲である。好ましくは１０，０００〜９０，０００の範囲である。５，０００未満の場合、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の耐衝撃性は向上するものの光沢が若干劣り、光沢の優れるゴム変性耐衝撃性樹脂組成物を得ようとするならば５，０００以上が好ましい。また、１５０，０００を越えると、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の光沢は良好であるが耐衝撃強度が劣り好ましくない。更に、ゴム状重合体組成物は粉末状になり易く、しかも成形性が悪くベール状になりにくいという問題が発生して好ましくない。
【００２０】
次に、本発明におけるブロック共重合体（ＩＩ）のゲルパーミエーションクロマトグラフで測定されるポリスチレン換算の重量平均分子量（Ｍｗ）は１〜３０万の範囲である。好ましくは５〜２０万の範囲である。重量平均分子量（Ｍｗ）が１万より小さいと、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、得られる樹脂の衝撃強度が劣る。また、ピーク分子量が３０万を超えると、ゴム変性耐衝撃性樹脂組成物の製造時に、芳香族ビニル単量体への溶解およびこの溶液の移送に多くの時間を費やす等、製造工程上大きな問題となる。さらに、ゴム状重合体組成物は粉末状になり易く、しかも成形性が悪くベール状になりにくいという問題が発生し好ましくない。
【００２１】
また、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比Ｍｗ／Ｍｎは１．１〜３．０の範囲が好ましい。
本発明のブロック共重合体（ＩＩ）中の全芳香族ビニル単量体含量は２５〜７５重量％の範囲である。好ましくは３５〜６０重量％の範囲である。２５重量％未満では、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、耐衝撃性は向上するものの光沢が若干劣り好ましくない。７０重量％を越えると、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の光沢は良好であるが耐衝撃強度が劣り好ましくない。
【００２２】
次に、本発明のゴム状重合体組成物中のブロックとなっている芳香族ビニル単量体含量は５〜７０重量％の範囲である。好ましくは１５〜６０重量％の範囲である。ブロックとなっている芳香族ビニル単量体含量が５重量％未満の場合、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の耐衝撃性は向上するものの光沢が若干劣り、光沢の優れるゴム変性耐衝撃性樹脂組成物を得ようとするならば５重量％以上が好ましい。また、７０重量％を越えると、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の光沢は良好であるが耐衝撃強度が劣り好ましくない。更に、ゴム状重合体組成物は粉末状になり易く、しかも成形性が悪くベール状になりにくいという問題が発生して好ましくない。
【００２３】
また、ゴム状重合体組成物中のブロックとなっている芳香族ビニル重合体のゲルパーミエーションクロマトグラフで測定されるポリスチレン換算の重量平均分子量（Ｍｗ）は５，０００〜１５０，０００の範囲である。好ましくは、１０，０００〜９０，０００の範囲である。５，０００未満の場合、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の耐衝撃性は向上するものの光沢が若干劣り、光沢の優れるゴム変性耐衝撃性樹脂組成物を得ようとするならば５，０００以上が好ましい。また、１５０，０００を越えると、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の光沢は良好であるが耐衝撃強度が劣り好ましくない。更に、ゴム状重合体組成物は粉末状になり易く、しかも成形性が悪くベール状になりにくいという問題が発生して好ましくない。
【００２４】
本発明のゴム状重合体組成物は、ブロック共重合体（Ｉ）２０〜９９重量部とブロック共重合体（ＩＩ）１〜８０重量部からなる組成物である。好ましくは、ブロック共重合体（Ｉ）５０〜９５重量部とブロック共重合体（ＩＩ）５０〜５重量部、更に好ましくは、ブロック共重合体（Ｉ）７０〜９５重量部とブロック共重合体（ＩＩ）３０〜５重量部からなる組成物である。
ブロック共重合体（ＩＩ）の割合が８０重量部を越えると、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の光沢と耐衝撃性のバランスにが劣り好ましくない。また、１重量％未満の場合、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、樹脂組成物の光沢が劣り好ましくない。
【００２５】
本発明のブロック共重合体（Ｉ）とブロック共重合体（ＩＩ）の混合物であるゴム状重合体組成物中の全芳香族ビニル単量体含量は５〜６０重量％の範囲である。好ましくは１５〜４０重量％の範囲である。５重量％未満では、ゴム状重合体組成物自体のコールドフローが著しく大きくなり、ゴムの貯蔵、輸送に問題が生じ、ゴムとしての取り扱いが困難となる。また、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、耐衝撃性は向上するものの光沢が若干劣り好ましくない。６０重量％を越えると、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合には、樹脂組成物の光沢は良好であるが耐衝撃強度が劣り好ましくない。
【００２６】
本発明のゴム状重合体組成物を構成するブロック共重合体（Ｉ）及びブロック共重合体（ＩＩ）は、少なくとも１種類の共役ジエン系単量体及び少なくとも１種類の芳香族ビニル単量体とを有機リチウム触媒の存在下で溶液重合させることにより製造することができる。本発明のゴム状重合体組成物の製造方法は、本発明の構造を有する組成物を得ることができれば、如何なる製造方法も採用することができる。
【００２７】
ブロック共重合体（Ｉ）の製造方法としては、例えば、炭化水素溶媒中、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてブロック共重合した後、引き続き、共役ジエン系単量体を添加し重合を完結させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてブロック共重合した後、引き続き、共役ジエン系単量体及び芳香族ビニル単量体を添加しランダム共重合させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてブロック共重合した後、引き続き、芳香族ビニル単量体を添加して芳香族ビニル単量体ブロックを増加させた後、更に共役ジエン系単量体を添加し重合を完結させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてブロック共重合した後、引き続き、芳香族ビニル単量体を添加して芳香族ビニル単量体ブロックを増加させた後、更に共役ジエン系単量体及び芳香族ビニル単量体を添加しランダム共重合させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてランダム共重合した後、引き続き、芳香族ビニル単量体を添加して芳香族ビニル単量体ブロックを形成した後に、更に共役ジエン系単量体を添加し重合を完結させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてランダム共重合した後、引き続き、芳香族ビニル単量体を添加して芳香族ビニル単量体ブロックを形成した後に、更に共役ジエン系単量体及び芳香族ビニル単量体を添加しランダム共重合させて製造する方法、等の溶液重合によって製造することができる。
【００２８】
ブロック共重合体（ＩＩ）の製造方法としては、例えば、炭化水素溶媒中、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてブロック共重合させて製造する方法、共役ジエン系単量体を有機リチウム触媒を用いて重合した後、引き続き、芳香族ビニル単量体を添加しブロック共重合させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてブロック共重合した後、引き続き、芳香族ビニル単量体を添加して芳香族ビニル単量体ブロックを増加させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてランダム共重合した後、引き続き、芳香族ビニル単量体を添加し、ブロック共重合させて製造する方法、等の溶液重合によって製造することができる。
【００２９】
また、炭化水素溶媒中、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてブロック共重合した後、アルコール等の公知の停止剤を添加し活性末端の一部を失活させ、引き続き、共役ジエン系単量体を添加し重合を完結させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてブロック共重合した後、アルコール等の公知の停止剤を添加し活性末端の一部を失活させ、引き続き、共役ジエン系単量体及び芳香族ビニル単量体を添加しランダム共重合させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてブロック共重合した後、アルコール等の公知の停止剤を添加し活性末端の一部を失活させ、引き続き、芳香族ビニル単量体を添加して芳香族ビニル単量体ブロックを増加させた後、更に共役ジエン系単量体を添加し重合を完結させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてブロック共重合した後、アルコール等の公知の停止剤を添加し活性末端の一部を失活させ、引き続き、芳香族ビニル単量体を添加して芳香族ビニル単量体ブロックを増加させた後、更に共役ジエン系単量体及び芳香族ビニル単量体を添加しランダム共重合させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてランダム共重合した後、アルコール等の公知の停止剤を添加し活性末端の一部を失活させ、引き続き、芳香族ビニル単量体を添加して芳香族ビニル単量体ブロックを形成した後に、更に共役ジエン系単量体を添加し重合を完結させて製造する方法、共役ジエン系単量体及び芳香族ビニル単量体の混合物を有機リチウム触媒を用いてランダム共重合した後、アルコール等の公知の停止剤を添加し活性末端の一部を失活させ、引き続き、芳香族ビニル単量体を添加して芳香族ビニル単量体ブロックを形成した後に、更に共役ジエン系単量体及び芳香族ビニル単量体を添加しランダム共重合させて製造する方法、等の溶液重合によって、ブロック共重合体（Ｉ）とブロック共重合体（ＩＩ）の本発明のゴム状重合体組成物を製造することができる。
【００３０】
また、上記の製造例において、アルコール等の公知の停止剤を添加する代わりに、純度の低い共役ジエン系単量体を添加し、その不純物によって活性末端の一部を失活させて、本発明のゴム状重合体組成物を製造することもできる。
溶液重合で用いる炭化水素溶媒の例としては、ブタン、ペンタン、ヘキサン等の脂肪族炭化水素、シクロペンタン、シクロヘキサン等の脂環族炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素が用いられる。好ましい例としては、ヘキサン、シクロヘキサンが挙げられる。
共役ジエン系単量体の例としては、１，３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、３−メチル−１，３−ペンタジエン、１，３−ヘプタジエン、１，３−ヘキサジエン等が挙げられ、一種又は二種以上を組み合わせて用いられる。好ましい単量体としては、１，３−ブタジエン、イソプレンが挙げられる。
【００３１】
また、芳香族ビニル系単量体の例としては、スチレン、ｐ−メチルスチレン、α−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、ジフェニルエチレン等が挙げられ、一種又は二種以上を組み合わせて用いられる。好ましい単量体としては、スチレンが挙げられる。
共役ジエン系単量体及び芳香族ビニル系単量体を重合するのに用いられる有機リチウム化合物とは、モノ有機リチウム化合物または多官能性有機リチウム化合物であり、あるいはモノ有機リチウム化合物と多官能性有機リチウム化合物との混合物であってもよい。
【００３２】
モノ有機リチウム化合物としては、例えばｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔｅｒｔ−ブチルリチウム、ｎ−プロピルリチウム、ｉｓｏ−プロピルリチウム、ベンジルリチウム等が挙げられるが、好ましくは、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウムが用いられる。
多官能性有機リチウム化合物としては、例えばジリチオメタン、１，４ージリチオブタン、１，６ージリチオヘキサン、１，４ージリチオシクロヘキセン、１，４ージリチオー２ーエチルシクロヘキサン、１，３ージリチオー４ーフェニルブタン、１，２ージリチオー１，２ージフェニルーエタン、１，１０ージリチオデカン、１，２０ージリチオエイコサン、１，１ージリチオジフェニレン、１，４ージリチオベンゼン、１，５ージリチオナフタレン、ジリチオポリブタジエン、ジリチオイソプレン、ジリチオジイソプレン、ジリチオポリイソプレン、等が挙げられる。
【００３３】
上記の他にモノ有機リチウム化合物と他の化合物を反応させることによって得られる実質的に多官能性有機リチウム化合物を含んでいる有機リチウム化合物であってもよい。これらの例のうち、特に代表的なものは、モノ有機リチウム化合物とポリビニル芳香族化合物の二者を含む反応生成物である。例えば、モノ有機リチウム化合物とポリビニル芳香族化合物との反応生成物，モノ有機リチウム化合物と共役ジエン系単量体と反応させた後、ポリビニル芳香族化合物と反応させた反応生成物、又はモノ有機リチウム化合物とモノビニル芳香族単量体を反応させた後、ポリビニル芳香族化合物と反応させた反応生成物，或いは、モノ有機リチウム化合物と共役ジエン系単量体又はモノビニル芳香族単量体、及びポリビニル芳香族化合物の三者を同時に反応させた反応生成物等が用いられる。さらに、モノ有機リチウム化合物とモノビニル芳香族との反応生成物に、ポリビニル芳香族化合物を反応させ、次いで、更にモノビニル芳香族化合物を反応して得られた触媒も有効である。
【００３４】
本発明におけるゴム状重合体組成物を、ゴム変性耐衝撃性樹脂組成物の強靱化剤として用いた場合、そのミクロ構造によって、得られる樹脂の耐衝撃性に若干の影響を与える。例えば、共役ジエン単量体としてブタジエンを用いる場合には、１，２−ビニル含量は５〜８０％、シス−１，４含量は１０〜８５％の範囲にあることが好ましいが、特に１，２−ビニル含量が１０〜４０％のものが好ましい。この範囲外の１，２−ビニル含量を有するゴム状重合体組成物を用いると、得られるゴム変性耐衝撃性樹脂組成物は衝撃強度が劣るものとなる。
【００３５】
これらの１，２−ビニル含量の調整法については特に制限がなく、従来のいかなる方法も用いることができ、例えば、共役ジエン系単量体の重合時、重合系にジメチルエーテル、ジエチルエーテル、テトラヒドロフラン、２，２−ビス（オキソラニル）プロパン、１，１−ビス（オキソラニル）エタン等のエーテル類；ジメチルアミンなどのアミン類；ジメチルスルフィド、ジエチルスルフィドなどのチオエーテル類を添加して重合を行うことによって達成される。
更に、ヘキサメチルホスホルアミド（ＨＭＰＡ）を添加する方法（特公昭４３−５９０４号公報）、テトラメチルエチレンジアミン（ＴＭＥＤＡ）を添加する方法（特公昭４２−１７１９９号公報）及びジエチレングリコールジメチルエーテルを添加する方法などがある。また、１，２−ビニル結合については分子鎖に均一になるように重合してもよく、あるいは、分子鎖に沿って漸減的に変化するように重合してもよく（特公昭４７−８７５号公報）、さらにはブロック的に結合するように重合してもよい（米国特許第３３０１８４０号明細書）。
【００３６】
１，２−ビニル結合を分子鎖中に均一になるように重合するには、通常重合開始温度を３０〜９０℃とし、できる限り定温重合する方法が採用され、また、１，２−ビニル結合を分子鎖に沿って漸減的に変化するように重合するためには、重合を昇温下で実施する方法、すなわち、通常重合開始温度を３０〜８０℃とし、重合終了温度を８５〜１２０℃とする方法、又は重合中に上記１，２ービニル含量調整剤を漸増的に添加する方法等が採用される。
【００３７】
本発明のゴム状重合体組成物の重合が終了した後、必要に応じて、水、無機酸または有機酸等で処理することもできる。
無機酸の例としては、硫酸、硝酸、リン酸、ホウ酸、炭酸等が挙げられる。有機酸は広い意味で酸性を有する有機化合物であってカルボン酸，スルホン酸，スルフイン酸などの化合物が挙げられるが、好ましくはカルボキシル基を有する有機化合物である。例えば、プロピオン酸，安息香酸、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラキン酸、シュウ酸、グルタル酸、アジピン酸、マロン酸、オレイン酸、リノール酸等あるいはこれらの混合物が挙げられる。これらの中でも、特に硫酸、炭酸、ホウ酸、ステアリン酸が好ましい。
【００３８】
該化合物の添加方法については、特に制限はないが、重合反応終了後、重合体溶液中にバッチ式もしくは連続式的に添加する方法が一般的に用いられる。
重合体溶液からの重合体の回収は、溶媒を除去する際に重合体が酸化劣化や熱的劣化を起こすのを防止するために安定剤を添加した後に、例えばスチームストリッピング、熱ロール、ドラムドライヤー乾燥、メタノール沈殿乾燥、真空乾燥等の公知の重合体分離法によって、本発明のゴム状重合体組成物を得ることができる。安定剤としては、従来から使用されてきた公知の安定剤のいずれでもよく、２，６−ジーｔｅｒｔ−ブチルー４−メチルフェノール、ｎ−オクタデシルー３−（３′，５′−ジーｔｅｒｔ−ブチルー４′−ヒドロキシフェニル）プロピオネート等のフェノール系化合物、トリスー（２，４−ジーｔｅｒｔ−ブチルフェニル）フォスファイト等の有機フォスファイト系化合物、４，６−ビス〔（オクチルチオ）メチル〕−Ｏ−クレゾール等の含イオウフェノール系化合物等の種々の酸化防止剤を一種又は二種以上組み合わせて使用することができる。
【００３９】
本発明のゴム変性耐衝撃性樹脂組成物は、上述したゴム状重合体組成物を２〜３０重量％含有するスチレン系樹脂組成物であり、２重量％未満のゴムの使用量では本発明が目的とする衝撃強度の改良効果が不十分であり、本発明の目的を達成するのが困難である。一方、３０重量％を超える使用量では衝撃強度は向上するものの本来のポリスチレン系樹脂の持つ特性、例えば、引張り強度、剛性、更に光沢等の外観特性を損なうものとなり好ましくない。また、グラフト重合溶液の粘度が非常に高くなり、本発明のゴム変性耐衝撃性樹脂組成物の製造が困難となる。
また、本発明のゴム状重合体組成物に他のゴム状重合体を混合したものを強靱化剤として使用することもできる。他のゴム状重合体としては、ポリブタジエンゴム、スチレンーブタジエンブロック共重合体、スチレンーブタジエンランダム共重合体等が挙げられ、本発明のゴム状重合体組成物に他のゴム状重合体を混合して使用する場合、その使用比率は、重量比で９５：５〜２０：８０の範囲で使用することが好ましい。
【００４０】
本発明において得られるゴム変性耐衝撃性樹脂組成物中に分散したゴム状重合体組成物ゴム粒子の平均粒子径は０．０５〜４．０μｍの範囲に調整することが好ましい。好ましくは０．１〜２．０μｍ、より好ましくは０．２〜１．５μｍの範囲である。平均粒子径が０．０５μｍ未満では、樹脂組成物の耐衝撃強度が劣り、４．０μｍを超える場合には、樹脂組成物の光沢が劣り好ましくない。
重合体のゴム粒子径の調整は、ゴム状重合体組成物を芳香族ビニル単量体、又は芳香族ビニル単量体と共重合可能な単量体との混合物に溶解し、塊状重合、塊状懸濁重合、溶液重合によりグラフト重合させる際、ゴム溶液に揃断応力がかかける条件、例えば攪拌機の回転数を変えることによってゴム粒子径を調整することができるが、本発明のゴム状重合体組成物を用いることによって、更に、小さなゴム粒子を得ることができる。
【００４１】
本発明のゴム変性耐衝撃性樹脂組成物を得る方法については、本発明の構成用件を満足しうるように配慮されている限り特に制限はなく、公知の方法を用いることができる。
通常、本発明のゴム状重合体組成物を芳香族ビニル単量体、又は芳香族ビニル単量体と共重合可能な単量体との混合物に溶解し、ゴム溶液に揃断応力がかかるように攪拌しながら、塊状重合法または塊状懸濁重合法または溶液重合法によりグラフト重合させ、芳香族ビニル系単量体、又は芳香族ビニル単量体と共重合可能な単量体をとの共重合体よりなるマトリックス中に、該ゴム状重合体組成物が粒子状に分散してなるゴム変性耐衝撃性樹脂組成物を得る方法が好ましい。
【００４２】
本発明で用いられる芳香族ビニル単量体としては、スチレン、ビニルナフタレン、α−メチルスチレン、αーエチルスチレン、α一メチルーｐ一メチルスチレンなどのα一アルキル置換スチレン、ｍ−メチルスチレン、ｐ一メチルスチレン、２，４−ジメチルスチレン、エチルビニルベンゼン、ｐ−ｔｅｒｔ一ブチルスチレン、などの核アルキル置換スチレン、モノクロルスチレン、ジクロルスチレン、トリブロモスチレン、テトラブロモスチレン等のハロゲン化スチレン、ｐーヒドロキシスチレン、ｏーメトキシスチレン等が挙げられ、１種又は２種以上の混合物として用いられる。これらのうち、スチレン、α一メチルスチレン、ｐ−メチルスチレンが好ましい。
芳香族ビニル単量体以外の共重合可能な単量体としては、不飽和ニトリル単量体、（メタ）アクリル酸エステル、その他共重合可能な単量体等から選ばれたものである。
【００４３】
不飽和ニトリル単量体の例としては、アクリロニトリル、メタアクリロニトリル等が挙げられ、１種又は２種以上の混合物として用いられる。特に、アクリロニトリルが好ましい。
（メタ）アクリル酸エステルの例としては、メチルアクリレート、エチルアクリレート、プロピルアクリレート、ブチルアクリレート、アミルアクリレート、ヘキシルアクリレート、オクチルアクリレート、ドデシルアクリレート、シクロヘキシルアクリレート、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、ブチルメタクリレート、アミルメタクリレート、ヘキシルメタクリレート、オクチルメタクリレート、ドデシルメタクリレート、シクロヘキシルメタクリレート等が挙げられ、１種又は２種以上の混合物として用いられる。特に、メチルメタクリレートが好ましい。
その他共重合可能な単量体としては、アクリル酸、メタクリル酸、酢酸ビニル、無水マレイン酸、Ｎ−メチルマレイミド，Ｎ−フェニルマレイミドなどが挙げられる。
【００４４】
また、本発明の樹脂組成物を得るに際し、前記の芳香族ビニル単量体、又は芳香族ビニル単量体と共重合可能な単量体との混合液に不活性溶媒を加えて重合を行なっても良い。不活性溶媒としては、エチルベンゼン、トルエンなどのほか、メチルエチルケトン、シクロヘキサノンなどの極性溶媒を１種又は２種以上使用しても良い。これらの不活性溶媒の量は、ゴム状重合体組成物を溶解したビニル単量体混合液１００重量部に対し、１００重量部以下が好ましく、５０重量部以下が更に好ましい。
本発明において、ゴム状重合体組成物を溶解した芳香族ビニル単量体、又は芳香族ビニル単量体と共重合可能な単量体との混合液をラジカル重合するに際し、有機過酸化物又はアゾ化合物の存在下で重合を行なうこともできる。
【００４５】
有機過酸化物としては、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）３，３，５−トリメチルシクロヘキサン等のパーオキシケタール類；ジ−ｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、ジクミルパーオキサイド等のジアルキルパーオキサイド類；ベンゾイルパーオキサイド、ｍ−トルオイルパーオキサオド、ラウロイルパーオキサイド等のジアシルパーオキサイド類；ジミリスチルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート等のパーオキシジカーボネート類；ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシアセテート、ジ−ｔ−ブチルジパーオキシイソフタレート、ｔ−ブチルパーオキシベンゾエート等のパーオキシエステル類；シクロヘキサノンパーオキサイド、メチルエチルケトンパーオキサイド等のケトンパーオキサイド類；ｐ−メンタハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド等のハイドロパーオキサイド類などが用いられる。また、アゾ化合物としては、アゾビスイソブチロニトリル、アゾビスシクロヘキサンカーボニトリル等が用いられる。これらは一種又は二種以上の組み合わせで用いられる。
有機過酸化物又はアゾ化合物の使用量は、前記ビニル単量体混合物中１０〜１，０００ｐｐｍの範囲が好ましい。
【００４６】
また、本発明において、公知の連鎖移動剤が用いられる。連鎖移動剤として、例えばｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン、α−メチルスチレンダイマー、１ーフェニルブテンー２ーフルオレン、ジペンテン、クロロホルム等のメルカプタン類、テルペン類、ハロゲン化合物等を用いることができる。
本発明の樹脂組成物において、公知の酸化防止剤、紫外線安定剤等の安定剤を添加しても良い。酸化防止剤としては、例えばオクタデシル−３−（３，５ージーｔーブチルー４ーヒドロキシフェニル）プロピオネート、２，６−ジーｔーブチルー４ーメチルフェノール、２ー（１ーメチルシクロヘキシル）ー４，６ージメチルフェノール、２，２’ーメチレンビス（４ーエチルー６ーｔーブチルフェノール）、４，４’ーチオビス（６ーｔ−ブチルー３ーメチルフェノール）、２，４−ビス［（オクチルチオ）メチル］−ｏ−クレゾール、トリエチレングリコールービス［３ー（３ーｔ−ブチルー５ーメチルー４ーヒドロキシフェニル）プロピオネート］、トリス（ジノニルフェニル）ホスファイト、トリスー（２，４ージーｔ−ブチルフェニル）ホスファイト等が挙げられ、その添加量は樹脂組成物１００重量部当たり、０．０１〜５重量部、好ましくは０．１〜２重量部である。
【００４７】
紫外線安定剤としては、例えば、２−（５−メチルー２−ヒドロキシフェニル）ベンゾトリアゾール、２一（３，５−ジ−ｔ−ブチル−２−ヒドロキシフェニル）ベンゾトリアゾールなどのトリアゾール系、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケートなどのヒンダードアミン系、その他にｐ−ｔ−ブチルフェニルサリシレート、２，２’−ジヒドロキシ−４−メトキシベンゾフェノンなどが挙げられる。特に好ましくはトリアゾール系、ヒンダードアミン系の単独又は併用系である。これらの紫外線安定剤の添加量は好ましくは樹脂組成物１００重量部当り０．０１〜５重量部、更に好ましくは０．０５〜２重量部である。
また、必要に応じて通常用いられる流動パラフィン、ミネラルオイル、有機ポリシロキサン等の内部潤滑剤を添加することも可能である。例えば、有機ポリシロキサンであるポリジメチルシロキサンを樹脂組成物１００重量部に対して０．００５〜１０重量部添加してもよい。
【００４８】
以上のようにして得られたゴム変性耐衝撃性樹脂組成物におけるゲル含有量（トルエン不溶分の含有量）は５〜７５重量％の範囲とすることが好ましく、更に好ましくは、１０〜５０重量％である。ゲル含有量が少なすぎると樹脂組成物の耐衝撃性が劣り、多すぎると樹脂組成物の流動性が低下して加工する上で好ましくない。また、樹脂組成物中のゲルのトルエン中での膨潤指数は５〜１５の範囲が好ましく、更に好ましくは、７〜１２である。膨潤指数が小さすぎると耐衝撃性が劣り、大きすぎると耐衝撃性が低下し、光沢性も悪化するので好ましくない。膨潤指数の制御は、ビニル単量体を塊状重合、塊状懸濁重合または溶液重合にてグラフト重合する際の最終反応率及び未反応単量体の脱揮温度などにより調整することができる。
マトリックス樹脂部分の分子量は、ゲルパーミエーションクロマトグラフで測定されるポリスチレン換算の重量平均分子量で７〜５０万が好ましく、より好ましくは、１０〜３０万の範囲である。７万未満のものは、耐衝撃性が低下し、５０万を越えるものは流動性が悪く加工する上で好ましくない。
【００４９】
更に、本発明で得られる樹脂組成物の加工に際し、必要に応じて、難燃剤及び難燃助剤を配合し、難燃処方を施すことが可能である。難燃剤としては、種々のタイプがあるが、従来公知の全ての難燃剤が含まれ、ハロゲン系難燃剤、リン系難燃剤等が有効である。例えば、デカブロモジフェニルオキシド、テトラブロモビスフエノールＡ、テトラブロモビスフェノールＡのオリゴマー、トリス−（２，３−ジブロモプロピルー１）イソシアヌレート、リン酸アンモニウム、赤リン、トリクレジルホスフェートなどが挙げられる。難燃助剤としては、例えば三酸化アンチモン、五酸化アンチモン、アンチモン酸ソーダ、三塩化アンチモン、五塩化アンチモン、ホウ酸亜鉛、メタホウ酸バリウム、酸化ジルコニウムなどが挙げられる。難燃剤は、好ましくは樹脂１００重量部当り５〜４０重量部用いられ、難燃助剤は、好ましくは樹脂１００重量部当り２〜２０重量部用いられる。
【００５０】
また、必要に応じて、滑剤、離型剤、充填剤、帯電防止剤、着色剤等の各種添加剤を配合することができる。
更に、他の熱可塑性樹脂、例えば一般用ポリスチレン、ＡＳ樹脂、ＡＢＳ樹脂、ＡＥＳ樹脂、ＭＢＳ樹脂、ポリフェニレンエーテル、ポリカーボネート、スチレン−ブタジエン共重合体、メチルメタクリレート・スチレン共重合体樹脂、無水マレイン酸・スチレン共重合体樹脂、ポリアミド樹脂、ポリエステル樹脂などと混合してもよい。これらの樹脂を加えることによって、耐熱性、剛性、耐衝撃性、外観性、塗装性などが付与され、その用途によってブレンド使用される。
【００５１】
本発明のゴム変性耐衝撃性樹脂組成物は、射出成形、押出成形等の加工方法で成形され、多種多様に実用上有用な製品となしうることができる。その用途は、電気製品、ＯＡ機器のキャビネット、ハウジングなどや、自動車の内外装部品、住宅・家具などの部品、放送・通信用アンテナ部品、その他多岐にわたって使用される。
【００５２】
【実施例】
以下に若干の実施例を示し、本発明の具体的な実施態様を示すが、これは本発明の技術内容をより具体的に説明するためのものであり、本発明を限定するものではない。
また、各種測定は下記の方法によった。
［ゴム状重合体の重量平均分子量］
ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によって測定、計算されたポリスチレン換算の分子量である。
【００５３】
（ＧＰＣ測定条件）
測定機種 Ｗａｔｅｒｓ社製 ＬＣ Ｍｏｄｕｌｅ１
溶媒 ＴＨＦ（テトラヒドロフラン）
カラム Polymer Laboratories社製 ＰＬゲル ×３本
カラム温度 ３５℃
送液流量 ０．７ｍｌ／ｍｉｎ
試料濃度 ０．１重量％
試料注入量 ０．１ｍｌ
検出器 昭和電工社製 Ｓｈｏｄｅｘ ＲＩ ＳＥ−６１
【００５４】
［ミクロ構造］
赤外分光光度計（パーキンエルマー製 ＦＴ−ＩＲ１６５０）を用いて、ハンプトン法［Analytical Chemistry,21,923(1949) ］にて測定した。
［結合スチレン含量］
紫外線分光光度計（日立ＵＶ２００) を用い、定法により測定した。
［ブロックスチレン含量］
ゴム状重合体組成物を四酸化オスミウムを触媒にしてｔーブチルハイドロパーオキサイドにより酸化分解する方法［I.M.Kolthoff,et.al.,J.Poym.Sci. １,429(1946)］により分解して得られるポリスチレン成分量を紫外線分光光度計（日立ＵＶ２００）を用いて測定し、分解前のゴム状重合体に対する重量％と表した。
【００５５】
［ブロックスチレン部の重量平均分子量］
ゴム状重合体を四酸化オスミウムを触媒にしてｔーブチルハイドロパーオキサイドにより酸化分解［I.M.Kolthoff,et.al.,J.Poym.Sci. １,4 29(1946)］して得られたポリスチレンをＧＰＣ（ゲルパーミエーションクロマトグラフィー）によって測定したポリスチレン換算の分子量である。
（ＧＰＣ測定条件）
測定機種 Ｗａｔｅｒｓ社製 ＬＣ Ｍｏｄｕｌｅ１
溶媒 ＴＨＦ（テトラヒドロフラン）
カラム Polymer Laboratories社製 ＰＬゲル ×３本
カラム温度 ３５℃
送液流量 ０．７ｍｌ／ｍｉｎ
試料濃度 ０．１重量％
試料注入量 ０．１ｍｌ
検出器 昭和電工社製 Ｓｈｏｄｅｘ ＲＩ ＳＥ−６１
【００５６】
［アイゾット衝撃強度］
得られた組成物を圧縮成形して、厚さ３．２ｍｍの試験片を作成し、ＪＩＳ−Ｋ−７１１０に従って測定した。
［光沢］
ＡＳＴＭ Ｄ−６３８に従ってゲート部とエンド部の光沢度（入射角６０°）を測定し平均した。
［ゴム粒子径］
得られた樹脂の超薄切片法による電子顕微鏡写真を撮影し、写真中のゴム粒子３００〜６００個の粒子径を測定して重量平均したものである。すなわち、平均ゴム粒子径＝ΣniＤi⁴／ΣniＤi³（ｎi は粒子径Ｄi のゴム粒子の個数である）で計算した。
【００５７】
〔スチレンーブタジエンブロック共重合体（Ｉ）の製造〕
▲１▼ 内容積１０ｌの撹拌装置及びジャケット付きのオートクレーブを洗浄乾燥し、窒素置換後、第１表に示した条件で、予め精製、乾燥した１，３ーブタジエンとスチレン、シクロヘキサン、１，２ービニル調整剤としてテトラヒドロフラン又はＮ, Ｎ, Ｎ’, Ｎ’ーテトラメチルエチレンジアミンを添加し、次いで、ｎ−ブチルリチウムを加えて重合を開始した。反応終了後、引き続いてブタジエンを添加し、更に重合を継続した。重合終了後、メタノールを添加してリビングポリマーを完全に失活させた。こうして得られたポリマー溶液に安定剤として、２，６ージーｔｅｒｔーブチルー４ーメチルフェノールをポリマー１００重量部当たり０．５重量部添加し、スチームストリッピングすることにより溶媒を除去し、脱水後、引き続き熱ロール（１１０℃）により乾燥させ、第４表に示すブロック共重合体（Ｉ）試料名▲１▼〜▲４▼のスチレンーブタジエンブロック共重合体を得た。
【００５８】
▲２▼ 内容積１０ｌの撹拌装置及びジャケット付きのオートクレーブを洗浄乾燥し、窒素置換後、第１表に示した条件で、予め精製、乾燥した１，３ーブタジエン、スチレンとシクロヘキサン、１，２ービニル調整剤としてテトラヒドロフランを添加し、次いで、ｎ−ブチルリチウムを加えて重合を開始した。重合終了後、引き続いてスチレンを添加して重合を継続し、重合終了後、更にブタジエンを添加し、更に重合を継続した。重合終了後、メタノールを添加してリビングポリマーを完全に失活させた。こうして得られたポリマー溶液に安定剤として、２，６ージーｔｅｒｔーブチルー４ーメチルフェノールをポリマー１００重量部当たり０．５重量部添加し、スチームストリッピングすることにより溶媒を除去し、脱水後、引き続き熱ロール（１１０℃）により乾燥させ、第４表に示すブロック共重合体（Ｉ）試料名▲５▼のスチレンーブタジエンブロック共重合体を得た。
【００５９】
▲３▼ 内容積１０ｌの撹拌装置及びジャケット付きのオートクレーブを洗浄乾燥し、窒素置換後、第１表に示した条件で、予め精製、乾燥した１，３ーブタジエンとスチレン、シクロヘキサン、１，２ービニル調整剤としてテトラヒドロフランを添加し、次いで、ｎ−ブチルリチウムを加えて重合を開始した。重合終了後、引き続いてスチレンとブタジエンを添加して重合を継続した。重合終了後、メタノールを添加してリビングポリマーを完全に失活させた。こうして得られたポリマー溶液に安定剤として、２，６ージーｔｅｒｔーブチルー４ーメチルフェノールをポリマー１００重量部当たり０．５重量部添加し、スチームストリッピングすることにより溶媒を除去し、脱水後、引き続き熱ロール（１１０℃）により乾燥させ、第４表に示すブロック共重合体（Ｉ）試料名▲６▼、▲７▼、▲８▼のスチレンーブタジエンブロック共重合体を得た。
【００６０】
▲４▼ 内容積１０ｌの撹拌装置及びジャケット付きのオートクレーブを洗浄乾燥し、窒素置換後、第１表に示した条件で、予め精製、乾燥した１，３ーブタジエン、シクロヘキサン、１，２ービニル調整剤としてテトラヒドロフランを添加し、次いで、ｎ−ブチルリチウムを加えて重合を開始した。重合終了後、引き続いてスチレンを添加して重合を継続した。重合終了後、更にブタジエンを添加して、更に重合を継続した。重合終了後、メタノールを添加してリビングポリマーを完全に失活させた。こうして得られたポリマー溶液に安定剤として、２，６ージーｔｅｒｔーブチルー４ーメチルフェノールをポリマー１００重量部当たり０．５重量部添加し、スチームストリッピングすることにより溶媒を除去し、脱水後、引き続き熱ロール（１１０℃）により乾燥させ、第４表に示すブロック共重合体（Ｉ）試料名▲９▼のスチレンーブタジエンブロック共重合体を得た。
以上、▲１▼〜▲４▼で得られたスチレンーブタジエンブロック共重合体中のＡＳ( ブロックＡ中のスチレン含量）、ＣＳ（ブロックＣ中のスチレン含量）は、初期モノマー（ブタジエン／スチレン）の重合終了後のゴム状重合体組成物のスチレン含量、ブロックスチレン含量から計算して求めた。
【００６１】
〔スチレンーブタジエンブロック共重合体（ＩＩ）の製造〕
▲１▼ 内容積１０ｌの撹拌装置及びジャケット付きのオートクレーブを洗浄乾燥し、窒素置換後、第２表に示した条件で、予め精製、乾燥した１，３ーブタジエンとスチレン、シクロヘキサン、１，２ービニル調整剤としてテトラヒドロフラン又はＮ, Ｎ, Ｎ’, Ｎ’ーテトラメチルエチレンジアミンを添加し、次いで、ｎ−ブチルリチウムを加えて重合を開始した。重合終了後、メタノールを添加してリビングポリマーを完全に失活させた。こうして得られたポリマー溶液に安定剤として、２，６ージーｔｅｒｔーブチルー４ーメチルフェノールをポリマー１００重量部当たり０．５重量部添加し、スチームストリッピングすることにより溶媒を除去し、脱水後、引き続き熱ロール（１１０℃）により乾燥させ、第５表に示すブロック共重合体（ＩＩ）試料Ａ、Ｂ、Ｄのスチレンーブタジエンブロック共重合体を得た。
【００６２】
▲２▼ 内容積１０ｌの撹拌装置及びジャケット付きのオートクレーブを洗浄乾燥し、窒素置換後、第２表に示した条件で、予め精製、乾燥した１，３ーブタジエンとシクロヘキサン、１，２ービニル調整剤としてテトラヒドロフラン又はＮ, Ｎ, Ｎ’, Ｎ’ーテトラメチルエチレンジアミンを添加し、次いで、ｎ−ブチルリチウムを加えて重合を開始した。重合終了後、引き続いてスチレンを添加し、更に重合を継続した。重合終了後、メタノールを添加してリビングポリマーを完全に失活させた。こうして得られたポリマー溶液に安定剤として、２，６ージーｔｅｒｔーブチルー４ーメチルフェノールをポリマー１００重量部当たり、０．５重量部添加し、スチームストリッピングすることにより溶媒を除去し、脱水後、引き続き熱ロール（１１０℃）により乾燥させ、第５表に示すブロック共重合体（ＩＩ）試料Ｃのスチレンーブタジエンブロック共重合体を得た。
【００６３】
〔ゴム状重合体組成物の製造〕
▲１▼ 内容積１０ｌの撹拌装置及びジャケット付きのオートクレーブを洗浄乾燥し、窒素置換後、第３表に示した条件で、予め精製、乾燥した１，３ーブタジエンとスチレン、シクロヘキサン、１，２ービニル調整剤としてテトラヒドロフラン又はＮ, Ｎ, Ｎ’, Ｎ’ーテトラメチルエチレンジアミンを添加し、次いで、ｎ−ブチルリチウムを加えて重合を開始した。反応終了後、メタノールを添加して、リビングポリマーの一部を失活させた。その後、更に、ブタジエンを添加し、重合を継続した。重合終了後、メタノールを添加してリビングポリマーを完全に失活させた。こうして得られたポリマー溶液に安定剤として、２，６ージーｔｅｒｔーブチルー４ーメチルフェノールをポリマー１００重量部当たり、０．５重量部添加し、スチームストリッピングすることにより溶媒を除去し、脱水後、引き続き熱ロール（１１０℃）により乾燥させ、第６表に示すブロック共重合体（Ｉ）とブロック共重合体（ＩＩ）のゴム状重合体組成物▲１▼−Ａ、▲２▼−Ｂを得た。
ブロック共重合体（Ｉ）とブロック共重合体（ＩＩ）の性状は、それぞれの共重合体をＧＰＣカラムによって分取して分析した。また、それぞれの成分の重量比は、ＧＰＣの分子量分布曲線の面積比から求めた。
【００６４】
【表１】

【００６５】
【表２】

【００６６】
【表３】

【００６７】
【表４】

【００６８】
【表５】

【００６９】
【表６】

【００７０】
（実施例１〜１０）
耐衝撃性スチレン樹脂組成物の製造
第４〜６表に示した各種重合体を用いて、以下に述べる塊状重合法により耐衝撃性スチレン系樹脂組成物を得た。
攪拌装置、ジャケット付き反応器に第７表に示すような種類、割合でエチルベンゼン、スチレンを加え、次いで第４〜６表に示すブロック共重合体および安定剤として、ｎ−オクタデシルー３ー（３’，５’ージーｔｅｒｔーブチルー４’ーヒドロキシフェニル）プロピオネート０．３重量部、ｔ−ドデシルメルカプタン０．０５重量部を添加し、攪拌して溶解した。
これに、ジーｔｅｒｔーブチルパーオキサイドをモノマー１モルに対して１×１０^-4モル添加し１１０℃で３時間、１４０℃で５時間、１８０℃で２時間重合を行った。更に、２３０℃で３０分間加熱後、未反応生成物を減圧除去した後、得られた重合体を粉砕し、押出機にてペレット状にした。得られた耐衝撃性スチレン系樹脂組成物の物性を第７表に示す。実施例の結果からも明らかなように、本発明の重合体を用いて製造した耐衝撃性スチレン系樹脂組成物は、光沢と衝撃強度のバランスに優れていることがわかる。
【００７１】
（実施例１１）
ＡＢＳ樹脂の製造
実施例１と同様な反応器を用い、第７表に示すような種類、割合でエチルベンゼン、スチレン、アクリロニトリルを加え、次いでブロック共重合体および安定剤として、ｎ−オクタデシルー３ー（３^' ，５^' ージーｔｅｒｔーブチルー４^' ーヒドロキシフェニル）プロピオネート０．３重量部、ｔ−ドデシルメルカプタン０．０５重量部を添加し、攪拌して溶解した。
これに、ジーｔｅｒｔーブチルパーオキサイドをモノマー１モルに対して１×１０^-4モル添加し１１０℃で３時間、１４０℃で５時間、１８０℃で２時間重合を行った。更に、２３０℃で３０分間加熱後、未反応生成物を減圧除去した後、得られた重合体を粉砕し押出機にてペレット状にしてＡＢＳ樹脂を得た。
得られたＡＢＳ樹脂組成物の物性を第７表に示す。発明のスチレンーブタジエンブロック共重合体を用いて製造したＡＢＳ樹脂は、ゴム粒子径が小さくなり、光沢と衝撃強度のバランスに優れていることがわかる。
【００７２】
（実施例１２）
ＭＢＳ樹脂の製造
実施例１と同様な反応器を用い、第７表に示すような種類、割合でエチルベンゼン、スチレン、メチルメタクリレートを加え、次いでゴムおよび安定剤として、ｎ−オクタデシルー３ー（３’，５’ージーｔｅｒｔーブチルー４’ーヒドロキシフェニル）プロピオネート０．３重量部、ｔ−ドデシルメルカプタン０．０５重量部を添加し、攪拌して溶解した。
これに、ジーｔｅｒｔーブチルパーオキサイドをモノマー１モルに対して１×１０^-4モル添加し１１０℃で３時間、１４０℃で５時間、１８０℃で２時間重合を行った。更に、２３０℃で３０分間加熱後、未反応生成物を減圧除去した後、得られた重合体を粉砕し押出機にてペレット状にしてＭＢＳ樹脂を得た。
【００７３】
（比較例１、２、３）
耐衝撃性スチレン系樹脂組成物の製造
第８表に示した各種重合体を用いて、実施例１と同様な方法によって耐衝撃性スチレン系樹脂組成物を得た。
得られた耐衝撃性スチレン系樹脂組成物の物性を第８表に示す。本発明の範囲外のゴム状重合体組成物を用いた場合、衝撃強度、又は光沢が劣り、両方に優れた耐衝撃性スチレン系樹脂組成物は得られなかった。
【００７４】
【表７】

【００７５】
【表８】

【００７６】
【発明の効果】
本発明の特定の構造を有するゴム状重合体組成物は、従来にない構造を有するものであり、特に耐衝撃性スチレン系樹脂組成物の強靱化剤として用いた場合、従来の耐衝撃性スチレン系樹脂組成物と比較して、耐衝撃性と光沢との物性バランスに著しく優れたものが得られ、ＴＶ、ＶＴＲ等の電子機器、エアコン、冷蔵庫等の家庭電気製品、ＯＡ事務機器等の一般機器、文具、玩具、レジャースポーツ用品、家庭用品、建材・住宅部品、食品容器など広範囲に多種多様な用途に使用し得る、という工業的にも優れた効果を奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a rubber-like polymer composition having a specific structure, and a rubber-modified impact-resistant resin composition using the rubber-like polymer composition. When the rubbery polymer composition of the present invention is used as a toughening agent for a rubber-modified impact-resistant resin composition, a rubber-modified impact-resistant resin composition having a remarkably excellent balance between impact strength and gloss can be obtained. .
[0002]
[Prior art]
Polystyrene is used in various applications because it has excellent rigidity, transparency, gloss and the like and has good moldability. However, this polystyrene has a major drawback of being inferior in impact resistance, and various unvulcanized rubbers are used as toughening agents in order to improve this drawback. Among them, an impact-resistant styrene resin composition obtained by radical polymerization of a styrene monomer in the presence of unvulcanized rubber and graft polymerization to a rubber-like polymer has been widely produced industrially.
[0003]
As the unvulcanized rubber used for this purpose, there are polybutadiene and styrene-butadiene copolymer. In particular, polybutadiene is widely used for imparting excellent impact resistance.
In recent years, as the use of impact-resistant styrenic resin compositions has expanded to household electrical equipment housings and other parts, axle parts, office equipment parts, household goods, toys, etc. There has been a strong demand for an impact-resistant styrenic resin composition having an excellent balance between appearance characteristics and impact resistance.
In general, a resin composition is produced by dissolving a polybutadiene rubber or a styrene-butadiene copolymer rubber in a styrene monomer as a rubber-like polymer, and stirring or bulk-polymerizing or bulk-suspension polymerization. It is.
[0004]
In general, the impact resistance can be improved by increasing the content of the rubbery polymer, but the styrene resin with the increased rubbery polymer improves the impact strength but lowers the gloss. . On the other hand, the gloss can be improved by reducing the content of the rubber-like polymer or by making the rubber-like polymer particles dispersed in the resin fine, but the impact resistance is remarkably lowered.
Conventionally, as a method for improving the impact-resistant styrene resin composition, the solution viscosity of the conjugated diene polymer is specified (Japanese Patent Publication No. 58-4934), and the relationship between the solution viscosity of the conjugated diene polymer and Mooney viscosity. Specification (Japanese Examined Patent Publication No. 53-44188), specification of the relationship between the solution viscosity of the conjugated diene polymer and the tensile modulus and swelling degree of the organic peroxide crosslinked product (Japanese Patent Laid-Open No. 60-2501) Etc. have been proposed. However, in these methods, the balance between impact resistance and gloss is improved as compared with the case of using conventional polybutadiene, but it is not always satisfactory.
[0005]
On the other hand, JP-A-61-143415, JP-A-63-165413, JP-A-2-132112, JP-A-2-208312, etc. describe styrene-butadiene block copolymer having a specific structure. Methods have been proposed for improving impact resistance and appearance characteristics using coalescence. However, when these methods are examined in detail, the present situation is that a practically satisfactory balance between impact resistance and appearance characteristics has not been obtained.
[0006]
As another impact-resistant styrene-based resin composition, a rubber-modified styrene-acrylonitrile copolymer generally known as an ABS resin is known. Conventionally, an ABS resin is produced by an emulsion polymerization method in which styrene and acrylonitrile are graft-polymerized on a rubber latex adjusted to a desired particle size and degree of crosslinking, and is advantageous in that it has excellent gloss and impact resistance. However, the emulsion polymerization method can obtain an ABS resin excellent in gloss, impact strength, and rigidity, but the process is complicated and it is not economical because it consumes a large amount of energy. There were problems such as the need for processing.
In recent years, a mass ABS resin produced by dissolving a rubber-like polymer in a mixture of styrene and acrylonitrile and stirring or mass-polymerizing or mass-suspension polymerization has been discolored and colored with less impurities such as emulsifiers in the resin. It is attracting attention because it is difficult, and there is no need for wastewater treatment, etc., and it is economically advantageous.
However, since the mass ABS resin has a large dispersed rubber particle size, and the grafting of styrene and acrylonitrile to the rubbery polymer is not sufficient, it has gloss and impact strength as compared with the ABS resin obtained by the emulsion polymerization method. Has disadvantages such as inferiority.
[0007]
As a method for improving such drawbacks, a method using a rubber-like polymer having a low solution viscosity (JP-A 63-199717, JP-A 63-207803), a specific styrene-butadiene block copolymer There has been proposed a method using the method (Japanese Patent Laid-Open No. 2-185509). However, in these methods, a mass ABS resin that is satisfactory in terms of balance between gloss and impact strength has not been obtained.
As described above, in the conventional polybutadiene rubber and styrene-butadiene copolymer, a satisfactory impact-resistant styrene-based resin composition has not been obtained.
[0008]
[Problems to be solved by the invention]
As described above, when a conventional rubbery polymer is used for an impact-resistant styrenic resin, it has been difficult to improve the conflicting balance between impact resistance and gloss to a satisfactory level. The present invention solves the above-mentioned problems and provides a rubber-like polymer composition having a specific structure and a rubber-modified impact-resistant resin composition that greatly improves the balance between physical properties of impact resistance and gloss. It is.
[0009]
[Means for Solving the Invention]
The present inventors have studied in detail about obtaining a rubber-modified impact-resistant resin composition having an excellent balance between impact resistance and gloss, and as a result, have a specific structure that has not been studied as a conventional toughening agent. The present inventors have found that the above-described object can be achieved by a polymer composition, and have completed the present invention.
[0010]
That is, the present invention has the following general formula:
Block copolymer (I): (A1-B1-C) n
Block copolymer (II): (A2-B2) n
(Wherein n is an integer of 1 or more, block A1 is a random copolymer composed of a conjugated diene monomer and an aromatic vinyl monomer, and block B1 is a polymer composed of an aromatic vinyl monomer, block C is a polymer comprising a conjugated diene monomer or a random copolymer comprising a conjugated diene monomer and an aromatic vinyl monomer, and block A2 is a polymer or conjugated diene comprising a conjugated diene monomer. (A random copolymer composed of a monomer and an aromatic vinyl monomer, and block B2 is a polymer composed of an aromatic vinyl monomer.)
A rubbery polymer composition comprising 50 to 99 parts by weight of a block copolymer (I) represented by: 1 to 50 parts by weight of a block copolymer (II),
(1) Weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatograph of block copolymer (I) is 100,000 to 700,000, (2) wholly aromatic in block copolymer (I) Vinyl monomer content (TS) of 5 to 60% by weight,
(3) The aromatic vinyl monomer content (BS) which is the block in the block copolymer (I) is 5 to 50% by weight,
(4) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the aromatic vinyl polymer that is the block in the block copolymer (I) is 5,000 to 150,000,
(A) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the block copolymer (II) is 5 to 350,000,
(B) Total aromatic vinyl monomer content (TS) in the block copolymer (II) is 25 to 70% by weight,
(C) The aromatic vinyl monomer content (BS) which is a block in the block copolymer (II) is 5 to 70% by weight,
(D) The polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography of the aromatic vinyl polymer that is the block in the block copolymer (II) is 5,000 to 150,000,
75 to 98 wt.% Of a mixture of a rubber-like polymer composition and a monomer mainly composed of an aromatic vinyl monomer or a monomer copolymerizable with an aromatic vinyl monomer A rubber-modified impact-resistant resin composition obtained by radical polymerization of a part and 2 to 25 parts by weight of a rubbery polymer by a bulk polymerization method, a bulk suspension polymerization method or a solution polymerization method, wherein the rubbery polymer Provides a rubber-modified impact-resistant resin composition characterized by being a rubber-like polymer composition having the above structure.
[0011]
That is, the present invention has the following general formula:
Block copolymer (I): A1-B1-C
Block copolymer (II): A2-B2
(In the formula The Lock A1 is a random copolymer composed of a conjugated diene monomer and an aromatic vinyl monomer, Block B1 is a polymer composed of an aromatic vinyl monomer, and Block C is a polymer composed of a conjugated diene monomer. Random copolymer comprising a conjugated diene monomer and an aromatic vinyl monomer, block A2 is a polymer comprising a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer Block B2 is a polymer comprising an aromatic vinyl monomer. )
A rubbery polymer composition comprising 50 to 99 parts by weight of a block copolymer (I) represented by: 1 to 50 parts by weight of a block copolymer (II),
(1) Polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatograph of block copolymer (I) is 100,000 to 700,000.
(2) The total aromatic vinyl monomer content (TS) in the block copolymer (I) is 5 to 60% by weight,
(3) The content of aromatic vinyl monomer (BS) in the block copolymer (I) is 5 to 50% by weight,
(4) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the aromatic vinyl polymer that is the block in the block copolymer (I) is 5,000 to 150,000. ,
(A) Polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatograph of block copolymer (II) is 5 to 350,000,
(B) The total aromatic vinyl monomer content (TS) in the block copolymer (II) is 25 to 70% by weight,
(C) Aromatic vinyl monomer content (BS) which is a block in the block copolymer (II) is 5 to 70% by weight,
(D) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the aromatic vinyl polymer that is the block in the block copolymer (II) is 5,000 to 150,000. ,
75 to 98 wt.% Of a mixture of a rubber-like polymer composition and a monomer mainly composed of an aromatic vinyl monomer or a monomer copolymerizable with an aromatic vinyl monomer A rubber-modified impact-resistant resin composition obtained by radical polymerization of 2 to 25 parts by weight of a rubber-like polymer with a bulk polymerization method, a bulk suspension polymerization method or a solution polymerization method, wherein the rubber-like polymer Provides a rubber-modified impact-resistant resin composition characterized by being a rubber-like polymer composition having the above structure.
[0012]
Block copolymer (I) having a structure of A1-B1-C, A1-B1-C-A1-B1-C, wherein n is 1 or 2, A2-B2, A2-B2-A2-B2 A rubbery polymer composition of copolymer (II) is preferred. When n is 2 or more, the blocks A1, A2, B1, B2, and C may have the same structure or different structures.
[0013]
The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the block copolymer (I) in the present invention is in the range of 100,000 to 700,000. Preferably it is the range of 10-450,000. More preferably, it is the range of 150-400,000. When the weight average molecular weight (Mw) is less than 100,000, the impact strength of the resulting resin is inferior when used as a toughening agent for a rubber-modified impact-resistant resin composition. Further, when the weight average molecular weight exceeds 700,000, when used as a toughening agent for the rubber-modified impact-resistant resin composition, during the production of the rubber-modified impact-resistant resin composition, This is a major problem in the manufacturing process, such as spending a lot of time for transferring the solution. Furthermore, the rubber-like polymer composition is not preferable because it tends to be powdery and has a problem of poor moldability and difficulty in forming a veil.
The ratio Mw / Mn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably in the range of 1.1 to 3.0.
[0014]
The aromatic vinyl monomer content (AS) of block A1 in the block copolymer (I) of the present invention and the aromatic vinyl monomer content (CS) of block C in the block copolymer (I) are: It is preferable that the following relational expression (1) is satisfied.
[0015]
[Formula 1]

However, TS = AS + BS + CS
(TS represents the aromatic vinyl monomer content in the block copolymer (I), and BS represents the aromatic vinyl monomer content in the block copolymer (I) as a block.)
That is, 50% by weight or more of the non-blocked aromatic vinyl monomer content (TS-BS) in the block copolymer (I) is the block A1 (conjugated diene monomer and aromatic vinyl monomer). In a random copolymer consisting of a body). Preferably, it is the range of 1.0-0.7.
[0016]
Further, the block A1 or the block C which is an aromatic vinyl-conjugated diene random copolymer has an aromatic vinyl monomer block of less than 5% by weight based on the block copolymer (I). Also good.
The weight ratio of the conjugated diene monomer and the aromatic vinyl monomer in the block A1 in the block copolymer (I) is preferably in the range of 95: 5 to 20:80. More preferably, it is the range of 70: 30-30: 70. The weight ratio of the conjugated diene monomer to the aromatic vinyl monomer in the aromatic vinyl-conjugated diene random copolymer block C is preferably in the range of 100: 0 to 30:70. More preferably, it is the range of 100: 0-50: 50.
[0017]
The total aromatic vinyl monomer content in the block copolymer (I) of the present invention is in the range of 5 to 60% by weight. Preferably it is the range of 15 to 45 weight%. If it is less than 5% by weight, the cold flow of the rubber-like polymer composition itself is remarkably increased, causing problems in storage and transportation of the rubber, and handling as a rubber becomes difficult. When used as a toughening agent for a rubber-modified impact-resistant resin composition, the impact resistance is improved, but the gloss is slightly inferior. When it exceeds 60% by weight, when used as a toughening agent for a rubber-modified impact-resistant resin composition, the gloss of the resin composition is good but the impact strength is inferior.
[0018]
Next, the content of the aromatic vinyl monomer as a block in the block copolymer (I) of the present invention is in the range of 5 to 50% by weight. Preferably it is the range of 10-30 weight%. When the content of the aromatic vinyl monomer in the block is less than 5% by weight, when used as a toughening agent for the rubber-modified impact-resistant resin composition, the impact resistance of the resin composition is improved but the gloss is improved. If it is intended to obtain a rubber-modified impact-resistant resin composition that is slightly inferior and excellent in gloss, it is preferably 5% by weight or more. On the other hand, when it exceeds 50% by weight, when used as a toughening agent for a rubber-modified impact-resistant resin composition, the gloss of the resin composition is good but the impact strength is inferior. Furthermore, the rubber-like polymer composition is not preferable because it tends to be powdery and has a problem that the moldability is poor and it is difficult to form a veil.
[0019]
Moreover, the polystyrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatograph of the aromatic vinyl polymer which is the block in the block copolymer (I) is in the range of 5,000 to 150,000. It is. Preferably it is the range of 10,000-90,000. When it is less than 5,000, when used as a toughening agent for a rubber-modified impact-resistant resin composition, the impact resistance of the resin composition is improved, but the gloss is slightly inferior, and the rubber-modified impact-resistant resin composition is excellent in gloss. If it is going to obtain a thing, 5,000 or more are preferable. On the other hand, when it exceeds 150,000, when used as a toughening agent for a rubber-modified impact-resistant resin composition, the gloss of the resin composition is good, but the impact strength is inferior. Furthermore, the rubber-like polymer composition is not preferable because it tends to be powdery and has a problem that the moldability is poor and it is difficult to form a veil.
[0020]
Next, the polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography of the block copolymer (II) in the present invention is in the range of 1 to 300,000. Preferably it is the range of 5 to 200,000. When the weight average molecular weight (Mw) is less than 10,000, the impact strength of the resulting resin is inferior when used as a toughening agent for a rubber-modified impact-resistant resin composition. In addition, if the peak molecular weight exceeds 300,000, a large problem in the production process, such as spending a lot of time in dissolving the aromatic vinyl monomer and transferring this solution during the production of the rubber-modified impact-resistant resin composition It becomes. Furthermore, the rubber-like polymer composition is not preferable because it tends to be powdery and has a problem of poor moldability and difficulty in forming a veil.
[0021]
The ratio Mw / Mn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably in the range of 1.1 to 3.0.
The total aromatic vinyl monomer content in the block copolymer (II) of the present invention is in the range of 25 to 75% by weight. Preferably it is the range of 35-60 weight%. If it is less than 25% by weight, when used as a toughening agent for a rubber-modified impact-resistant resin composition, the impact resistance is improved, but the gloss is slightly inferior. When it exceeds 70% by weight, when used as a toughening agent for the rubber-modified impact-resistant resin composition, the gloss of the resin composition is good, but the impact strength is inferior.
[0022]
Next, the content of the aromatic vinyl monomer as a block in the rubbery polymer composition of the present invention is in the range of 5 to 70% by weight. Preferably it is the range of 15-60 weight%. When the content of the aromatic vinyl monomer in the block is less than 5% by weight, when used as a toughening agent for the rubber-modified impact-resistant resin composition, the impact resistance of the resin composition is improved but the gloss is improved. If it is intended to obtain a rubber-modified impact-resistant resin composition that is slightly inferior and excellent in gloss, it is preferably 5% by weight or more. On the other hand, if it exceeds 70% by weight, when used as a toughening agent for a rubber-modified impact-resistant resin composition, the gloss of the resin composition is good, but the impact strength is inferior. Furthermore, the rubber-like polymer composition is not preferable because it tends to be powdery and has a problem that the moldability is poor and it is difficult to form a veil.
[0023]
Moreover, the polystyrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatograph of the aromatic vinyl polymer which is the block in the rubber-like polymer composition is in the range of 5,000 to 150,000. is there. Preferably, it is the range of 10,000-90,000. When it is less than 5,000, when used as a toughening agent for a rubber-modified impact-resistant resin composition, the impact resistance of the resin composition is improved, but the gloss is slightly inferior, and the rubber-modified impact-resistant resin composition is excellent in gloss. If it is going to obtain a thing, 5,000 or more are preferable. On the other hand, when it exceeds 150,000, when used as a toughening agent for a rubber-modified impact-resistant resin composition, the gloss of the resin composition is good, but the impact strength is inferior. Furthermore, the rubber-like polymer composition is not preferable because it tends to be powdery and has a problem that the moldability is poor and it is difficult to form a veil.
[0024]
The rubbery polymer composition of the present invention is a composition comprising 20 to 99 parts by weight of the block copolymer (I) and 1 to 80 parts by weight of the block copolymer (II). Preferably, the block copolymer (I) 50 to 95 parts by weight and the block copolymer (II) 50 to 5 parts by weight, more preferably the block copolymer (I) 70 to 95 parts by weight and the block copolymer. (II) A composition comprising 30 to 5 parts by weight.
When the proportion of the block copolymer (II) exceeds 80 parts by weight, when used as a toughening agent for a rubber-modified impact-resistant resin composition, the balance between gloss and impact resistance of the resin composition is inferior. . On the other hand, when it is less than 1% by weight, the gloss of the resin composition is inferior when used as a toughening agent for the rubber-modified impact-resistant resin composition.
[0025]
The total aromatic vinyl monomer content in the rubbery polymer composition which is a mixture of the block copolymer (I) and the block copolymer (II) of the present invention is in the range of 5 to 60% by weight. Preferably it is the range of 15-40 weight%. If it is less than 5% by weight, the cold flow of the rubber-like polymer composition itself is remarkably increased, causing problems in storage and transportation of the rubber, and handling as a rubber becomes difficult. When used as a toughening agent for a rubber-modified impact-resistant resin composition, the impact resistance is improved, but the gloss is slightly inferior. When it exceeds 60% by weight, when used as a toughening agent for a rubber-modified impact-resistant resin composition, the gloss of the resin composition is good, but the impact strength is inferior.
[0026]
The block copolymer (I) and the block copolymer (II) constituting the rubbery polymer composition of the present invention include at least one conjugated diene monomer and at least one aromatic vinyl monomer. Can be produced by solution polymerization in the presence of an organolithium catalyst. As the method for producing the rubbery polymer composition of the present invention, any production method can be adopted as long as the composition having the structure of the present invention can be obtained.
[0027]
As a method for producing the block copolymer (I), for example, after block copolymerization of a mixture of a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent using an organolithium catalyst, A method in which a conjugated diene monomer is added to complete the polymerization, a mixture of a conjugated diene monomer and an aromatic vinyl monomer is block copolymerized using an organolithium catalyst, After adding block monomer and aromatic vinyl monomer to copolymerize randomly, after block copolymerizing mixture of conjugated diene monomer and aromatic vinyl monomer using organolithium catalyst Subsequently, after adding aromatic vinyl monomer to increase the aromatic vinyl monomer block, and further adding conjugated diene monomer to complete the polymerization, conjugated diene monomer After the block copolymerization of the mixture of the monomer and the aromatic vinyl monomer using the organolithium catalyst, the aromatic vinyl monomer block is increased by adding the aromatic vinyl monomer, followed by further conjugation. A method in which a diene monomer and an aromatic vinyl monomer are added and randomly copolymerized, and a mixture of a conjugated diene monomer and an aromatic vinyl monomer is randomly copolymerized using an organolithium catalyst. Subsequently, after the aromatic vinyl monomer is added to form the aromatic vinyl monomer block, the conjugated diene monomer is further added to complete the polymerization, and the conjugated diene monomer And a mixture of aromatic vinyl monomers are randomly copolymerized using an organolithium catalyst, followed by addition of aromatic vinyl monomers to form an aromatic vinyl monomer block, and further copolymerization. Process for preparing by random copolymerization was added diene monomer and aromatic vinyl monomer can be prepared by solution polymerization and the like.
[0028]
As a method for producing the block copolymer (II), for example, a method for producing a block copolymer of a mixture of a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent using an organolithium catalyst. , A method of polymerizing a conjugated diene monomer using an organolithium catalyst, followed by block copolymerization by adding an aromatic vinyl monomer, a conjugated diene monomer and an aromatic vinyl monomer Block copolymerization using an organolithium catalyst followed by addition of an aromatic vinyl monomer to increase the aromatic vinyl monomer block, a conjugated diene monomer and After a random copolymerization of a mixture of aromatic vinyl monomers using an organolithium catalyst, a solution weight such as a method in which an aromatic vinyl monomer is subsequently added and block copolymerized is produced. It can be produced by.
[0029]
In addition, after a block copolymerization of a mixture of a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent using an organolithium catalyst, a known terminator such as alcohol is added to add a part of the active terminal. , Followed by addition of conjugated diene monomer to complete polymerization, block copolymerization of mixture of conjugated diene monomer and aromatic vinyl monomer using organolithium catalyst After that, a known terminator such as alcohol is added to deactivate a part of the active terminal, and subsequently, a conjugated diene monomer and an aromatic vinyl monomer are added and randomly copolymerized, After block copolymerization of a mixture of a conjugated diene monomer and an aromatic vinyl monomer using an organolithium catalyst, a known terminator such as alcohol is added to deactivate a part of the active end, Aromatic bi A method of adding a conjugated monomer to increase the aromatic vinyl monomer block and then adding a conjugated diene monomer to complete the polymerization, a conjugated diene monomer and an aromatic vinyl After block copolymerization of the monomer mixture using an organolithium catalyst, a known terminator such as alcohol is added to deactivate a part of the active terminal, and then an aromatic vinyl monomer is added. A method of adding a conjugated diene monomer and an aromatic vinyl monomer and increasing the number of aromatic vinyl monomer blocks, followed by random copolymerization, a conjugated diene monomer and an aromatic vinyl monomer After random copolymerization of the mixture of monomers using an organolithium catalyst, a known terminator such as alcohol is added to deactivate part of the active terminal, and then aromatic vinyl monomer is added to add aromaticity. Group vinyl monomer block After completion of the polymerization, a method of adding a conjugated diene monomer to complete the polymerization, and a random copolymerization of a mixture of a conjugated diene monomer and an aromatic vinyl monomer using an organolithium catalyst Then, a known terminator such as alcohol is added to deactivate a part of the active terminal, and subsequently, an aromatic vinyl monomer is added to form an aromatic vinyl monomer block, and then a conjugated diene monomer is further added. The rubbery polymer of the present invention of block copolymer (I) and block copolymer (II) by solution polymerization such as a method of adding a monomer and an aromatic vinyl monomer to random copolymerize, etc. A composition can be produced.
[0030]
Further, in the above production example, instead of adding a known terminator such as alcohol, a conjugated diene monomer having a low purity is added, and a part of the active terminal is deactivated by the impurities, whereby the present invention It is also possible to produce a rubbery polymer composition.
Examples of hydrocarbon solvents used in solution polymerization include aliphatic hydrocarbons such as butane, pentane and hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. . Preferable examples include hexane and cyclohexane.
Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3 -Heptadiene, 1,3-hexadiene, etc. are mentioned, and they are used alone or in combination of two or more. Preferred monomers include 1,3-butadiene and isoprene.
[0031]
Examples of aromatic vinyl monomers include styrene, p-methyl styrene, α-methyl styrene, vinyl ethyl benzene, vinyl xylene, vinyl naphthalene, diphenyl ethylene, and the like, one or a combination of two or more. Used. A preferable monomer is styrene.
The organolithium compound used to polymerize the conjugated diene monomer and the aromatic vinyl monomer is a monoorganolithium compound or a polyfunctional organolithium compound, or a monoorganolithium compound and a polyfunctional compound. It may be a mixture with an organolithium compound.
[0032]
Examples of the monoorganolithium compound include n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, benzyllithium, etc., preferably n-butyllithium, sec -Butyl lithium is used.
Examples of the polyfunctional organolithium compound include dilithiomethane, 1,4-dilithiobutane, 1,6-dilithiohexane, 1,4-dilithiocyclohexene, 1,4-dilithio-2-ethylcyclohexane, 1,3-dilithio-4-phenylbutane, 1 , 2-dilithio-1,2-diphenyl-ethane, 1,10-dilithiodecane, 1,20-dilithioeicosane, 1,1-dilithiodiphenylene, 1,4-dilithiobenzene, 1,5-dilithionaphthalene, Examples include dilithiopolybutadiene, dilithioisoprene, dilithiodiisoprene, and dilithiopolyisoprene.
[0033]
In addition to the above, it may be an organic lithium compound containing a substantially multifunctional organic lithium compound obtained by reacting a monoorganolithium compound with another compound. Among these examples, a particularly representative one is a reaction product including two of a monoorganolithium compound and a polyvinyl aromatic compound. For example, a reaction product of a monoorganolithium compound and a polyvinyl aromatic compound, a reaction product obtained by reacting a monoorganolithium compound with a conjugated diene monomer, and then reacting with a polyvinyl aromatic compound, or monoorganolithium A reaction product obtained by reacting a compound with a monovinyl aromatic monomer and then reacting with a polyvinyl aromatic compound, or a monoorganolithium compound and a conjugated diene monomer or monovinyl aromatic monomer, and polyvinyl aroma A reaction product obtained by reacting three of the group compounds simultaneously is used. Further, a catalyst obtained by reacting a reaction product of a monoorganolithium compound and a monovinyl aromatic with a polyvinyl aromatic compound and then further reacting with the monovinyl aromatic compound is also effective.
[0034]
When the rubber-like polymer composition in the present invention is used as a toughening agent for a rubber-modified impact-resistant resin composition, the impact resistance of the resulting resin is slightly affected by its microstructure. For example, when butadiene is used as the conjugated diene monomer, the 1,2-vinyl content is preferably in the range of 5 to 80% and the cis-1,4 content is preferably in the range of 10 to 85%. Those having a 2-vinyl content of 10 to 40% are preferred. If a rubbery polymer composition having a 1,2-vinyl content outside this range is used, the resulting rubber-modified impact-resistant resin composition will be inferior in impact strength.
[0035]
There are no particular restrictions on the method for adjusting the 1,2-vinyl content, and any conventional method can be used. For example, during polymerization of a conjugated diene monomer, dimethyl ether, diethyl ether, tetrahydrofuran, Achieved by performing polymerization by adding ethers such as 2,2-bis (oxolanyl) propane and 1,1-bis (oxolanyl) ethane; amines such as dimethylamine; and thioethers such as dimethyl sulfide and diethyl sulfide. Is done.
Further, a method of adding hexamethylphosphoramide (HMPA) (Japanese Patent Publication No. 43-5904), a method of adding tetramethylethylenediamine (TMEDA) (Japanese Patent Publication No. 42-17199), and a method of adding diethylene glycol dimethyl ether and so on. The 1,2-vinyl bond may be polymerized so as to be uniform in the molecular chain, or may be polymerized so as to gradually change along the molecular chain (Japanese Patent Publication No. 47-875). In addition, it may be polymerized so as to bind in a block manner (US Pat. No. 3,318,840).
[0036]
In order to polymerize the 1,2-vinyl bond so that it is uniform in the molecular chain, a polymerization initiation temperature is usually set to 30 to 90 ° C., and a constant temperature polymerization method is employed as much as possible. In order to polymerize the polymer so as to gradually change along the molecular chain, the polymerization is carried out at an elevated temperature, that is, the polymerization initiation temperature is usually 30 to 80 ° C., and the polymerization end temperature is 85 to 120 ° C. Or a method in which the 1,2-vinyl content modifier is gradually added during the polymerization.
[0037]
After the polymerization of the rubbery polymer composition of the present invention is completed, it can be treated with water, an inorganic acid, an organic acid, or the like, if necessary.
Examples of inorganic acids include sulfuric acid, nitric acid, phosphoric acid, boric acid, carbonic acid and the like. The organic acid is an organic compound having acidity in a broad sense and includes compounds such as carboxylic acid, sulfonic acid and sulfinic acid, and is preferably an organic compound having a carboxyl group. For example, propionic acid, benzoic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oxalic acid, glutaric acid, adipic acid, malonic acid, oleic acid, linoleic acid, etc., or a mixture thereof It is done. Among these, sulfuric acid, carbonic acid, boric acid, and stearic acid are particularly preferable.
[0038]
The method for adding the compound is not particularly limited, but a method of batchwise or continuously adding to the polymer solution after completion of the polymerization reaction is generally used.
Recovery of the polymer from the polymer solution can be accomplished by adding a stabilizer to prevent the polymer from undergoing oxidative degradation or thermal degradation when removing the solvent, for example, steam stripping, hot roll, drum The rubbery polymer composition of the present invention can be obtained by a known polymer separation method such as dryer drying, methanol precipitation drying, or vacuum drying. As the stabilizer, any of known stabilizers conventionally used may be used. 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4 Phenolic compounds such as' -hydroxyphenyl) propionate, organic phosphite compounds such as tris (2,4-di-tert-butylphenyl) phosphite, 4,6-bis [(octylthio) methyl] -O-cresol, etc. These various antioxidants such as sulfur-containing phenol compounds can be used singly or in combination of two or more.
[0039]
The rubber-modified impact-resistant resin composition of the present invention is a styrenic resin composition containing 2 to 30% by weight of the rubbery polymer composition described above. The effect of improving the intended impact strength is insufficient, and it is difficult to achieve the object of the present invention. On the other hand, if the amount used exceeds 30% by weight, the impact strength is improved, but the properties of the original polystyrene resin such as tensile strength, rigidity, and appearance properties such as gloss are impaired, which is not preferable. In addition, the viscosity of the graft polymerization solution becomes very high, making it difficult to produce the rubber-modified impact-resistant resin composition of the present invention.
Moreover, what mixed other rubber-like polymers with the rubber-like polymer composition of this invention can also be used as a toughening agent. Other rubber-like polymers include polybutadiene rubber, styrene-butadiene block copolymer, styrene-butadiene random copolymer, etc., and other rubber-like polymers are mixed with the rubber-like polymer composition of the present invention. When used, the use ratio is preferably in the range of 95: 5 to 20:80 by weight.
[0040]
The average particle size of the rubber-like polymer composition rubber particles dispersed in the rubber-modified impact-resistant resin composition obtained in the present invention is preferably adjusted in the range of 0.05 to 4.0 μm. Preferably it is 0.1-2.0 micrometers, More preferably, it is the range of 0.2-1.5 micrometers. When the average particle diameter is less than 0.05 μm, the impact strength of the resin composition is inferior, and when it exceeds 4.0 μm, the gloss of the resin composition is inferior, which is not preferable.
The rubber particle size of the polymer is adjusted by dissolving the rubber-like polymer composition in an aromatic vinyl monomer or a mixture of monomers copolymerizable with the aromatic vinyl monomer, When graft polymerization is carried out by suspension polymerization or solution polymerization, the rubber particle diameter can be adjusted by changing the conditions under which the crushing stress is applied to the rubber solution, for example, by changing the rotational speed of the stirrer. By using the composition, smaller rubber particles can be obtained.
[0041]
The method for obtaining the rubber-modified impact-resistant resin composition of the present invention is not particularly limited as long as the constitutional requirements of the present invention are satisfied, and a known method can be used.
Usually, the rubber-like polymer composition of the present invention is dissolved in an aromatic vinyl monomer or a mixture of a monomer copolymerizable with an aromatic vinyl monomer, so that a crushing stress is applied to the rubber solution. The polymer is graft-polymerized by a bulk polymerization method, a bulk suspension polymerization method or a solution polymerization method with stirring, and an aromatic vinyl monomer or a monomer copolymerizable with an aromatic vinyl monomer is copolymerized. A method of obtaining a rubber-modified impact-resistant resin composition in which the rubber-like polymer composition is dispersed in the form of a polymer matrix is preferable.
[0042]
Examples of the aromatic vinyl monomer used in the present invention include styrene, vinyl naphthalene, α-methyl styrene, α-ethyl styrene, α-alkyl styrene such as α-methyl-p-methyl styrene, m-methyl styrene, p-methyl. Nuclear alkyl-substituted styrene such as styrene, 2,4-dimethyl styrene, ethyl vinyl benzene, p-tert-butyl styrene, halogenated styrene such as monochloro styrene, dichloro styrene, tribromo styrene, tetrabromo styrene, p-hydroxy Styrene, o-methoxystyrene, etc. are mentioned, and it is used as 1 type, or 2 or more types of mixtures. Of these, styrene, α-methylstyrene, and p-methylstyrene are preferred.
The copolymerizable monomer other than the aromatic vinyl monomer is selected from unsaturated nitrile monomers, (meth) acrylic acid esters, other copolymerizable monomers, and the like.
[0043]
Examples of the unsaturated nitrile monomer include acrylonitrile, methacrylonitrile and the like, and are used as one kind or a mixture of two or more kinds. In particular, acrylonitrile is preferred.
Examples of (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Examples thereof include amyl methacrylate, hexyl methacrylate, octyl methacrylate, dodecyl methacrylate, cyclohexyl methacrylate and the like, and they are used as one kind or a mixture of two or more kinds. In particular, methyl methacrylate is preferable.
Other copolymerizable monomers include acrylic acid, methacrylic acid, vinyl acetate, maleic anhydride, N-methylmaleimide, N-phenylmaleimide, and the like.
[0044]
In obtaining the resin composition of the present invention, an inert solvent is added to a mixed solution of the aromatic vinyl monomer or a monomer copolymerizable with the aromatic vinyl monomer to perform polymerization. May be. As the inert solvent, one or more polar solvents such as methyl ethyl ketone and cyclohexanone may be used in addition to ethylbenzene and toluene. The amount of these inert solvents is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the vinyl monomer mixed solution in which the rubber-like polymer composition is dissolved.
In the present invention, when radically polymerizing a liquid mixture of an aromatic vinyl monomer in which a rubber-like polymer composition is dissolved or a monomer copolymerizable with an aromatic vinyl monomer, an organic peroxide or Polymerization can also be carried out in the presence of an azo compound.
[0045]
Examples of the organic peroxide include peroxyketals such as 1,1-bis (t-butylperoxy) cyclohexane and 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane; Dialkyl peroxides such as t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide; benzoyl peroxide, m-toluoyl peroxide, lauroyl Diacyl peroxides such as peroxides; Peroxydicarbonates such as dimyristyl peroxydicarbonate and diisopropyl peroxydicarbonate; t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, di-t-butyldi Peroxyisophthalate, t-butyl -Peroxyesters such as oxybenzoate; Ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide; Hydroperoxides such as p-menta hydroperoxide, t-butyl hydroperoxide, cumene hydroperoxide, etc. Used. As the azo compound, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, or the like is used. These are used alone or in combination of two or more.
The amount of the organic peroxide or azo compound used is preferably in the range of 10 to 1,000 ppm in the vinyl monomer mixture.
[0046]
In the present invention, a known chain transfer agent is used. As the chain transfer agent, for example, n-dodecyl mercaptan, tert-dodecyl mercaptan, α-methylstyrene dimer, 1-phenylbutene-2-fluorene, dipentene, chloroform and other mercaptans, terpenes, halogen compounds and the like can be used.
In the resin composition of the present invention, stabilizers such as known antioxidants and ultraviolet stabilizers may be added. Examples of the antioxidant include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6- Dimethylphenol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 2,4-bis [(octylthio) methyl] -o-cresol , Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, etc. The amount added is 0.01 to 5 times per 100 parts by weight of the resin composition. Parts, preferably 0.1 to 2 parts by weight.
[0047]
Examples of the UV stabilizer include triazoles such as 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, and bis (2 , 2,6,6-tetramethyl-4-piperidyl) sebacate and the like, and pt-butylphenyl salicylate, 2,2′-dihydroxy-4-methoxybenzophenone and the like. Particularly preferred are triazole type and hindered amine type alone or in combination. The addition amount of these ultraviolet stabilizers is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, per 100 parts by weight of the resin composition.
Moreover, it is also possible to add internal lubricants such as liquid paraffin, mineral oil, and organic polysiloxane that are usually used as necessary. For example, you may add 0.005-10 weight part of polydimethylsiloxane which is organic polysiloxane with respect to 100 weight part of resin compositions.
[0048]
The gel content (content of insoluble toluene) in the rubber-modified impact-resistant resin composition obtained as described above is preferably in the range of 5 to 75% by weight, more preferably 10 to 50% by weight. %. If the gel content is too low, the impact resistance of the resin composition is inferior, and if it is too high, the fluidity of the resin composition is lowered, which is not preferable. Moreover, the swelling index in toluene of the gel in a resin composition has the preferable range of 5-15, More preferably, it is 7-12. If the swelling index is too small, the impact resistance is inferior, and if it is too large, the impact resistance is lowered and the glossiness is also deteriorated. The control of the swelling index can be adjusted by the final reaction rate and the devolatilization temperature of the unreacted monomer when the vinyl monomer is graft polymerized by bulk polymerization, bulk suspension polymerization or solution polymerization.
The molecular weight of the matrix resin portion is preferably from 700,000 to 500,000, more preferably from 100,000 to 300,000 in terms of polystyrene-converted weight average molecular weight measured by gel permeation chromatography. Those with less than 70,000 have poor impact resistance, and those with more than 500,000 are not preferable for processing due to poor fluidity.
[0049]
Furthermore, when processing the resin composition obtained in the present invention, it is possible to add a flame retardant and a flame retardant aid as necessary to give a flame retardant formulation. Although there are various types of flame retardants, all conventionally known flame retardants are included, and halogen flame retardants, phosphorus flame retardants and the like are effective. For example, decabromodiphenyl oxide, tetrabromobisphenol A, an oligomer of tetrabromobisphenol A, tris- (2,3-dibromopropyl-1) isocyanurate, ammonium phosphate, red phosphorus, tricresyl phosphate, etc. . Examples of the flame retardant aid include antimony trioxide, antimony pentoxide, sodium antimonate, antimony trichloride, antimony pentachloride, zinc borate, barium metaborate, and zirconium oxide. The flame retardant is preferably used in an amount of 5 to 40 parts by weight per 100 parts by weight of the resin, and the flame retardant aid is preferably used in an amount of 2 to 20 parts by weight per 100 parts by weight of the resin.
[0050]
Moreover, various additives, such as a lubricant, a mold release agent, a filler, an antistatic agent, a coloring agent, can be mix | blended as needed.
Further, other thermoplastic resins such as general-purpose polystyrene, AS resin, ABS resin, AES resin, MBS resin, polyphenylene ether, polycarbonate, styrene-butadiene copolymer, methyl methacrylate / styrene copolymer resin, maleic anhydride / You may mix with a styrene copolymer resin, a polyamide resin, a polyester resin, etc. By adding these resins, heat resistance, rigidity, impact resistance, appearance, paintability, and the like are imparted and blended depending on the application.
[0051]
The rubber-modified impact-resistant resin composition of the present invention is molded by a processing method such as injection molding or extrusion molding, and can be made into a wide variety of practically useful products. Its applications are used in a wide variety of applications such as electrical products, OA equipment cabinets, housings, automobile interior and exterior parts, parts for homes and furniture, broadcasting / communication antenna parts, and the like.
[0052]
【Example】
Some examples will be shown below, and specific embodiments of the present invention will be shown. However, this is intended to explain the technical contents of the present invention more specifically, and does not limit the present invention.
Various measurements were performed according to the following methods.
[Weight average molecular weight of rubbery polymer]
It is the molecular weight of polystyrene conversion measured and calculated by GPC (gel permeation chromatography).
[0053]
(GPC measurement conditions)
LC Model 1 manufactured by Waters
Solvent THF (tetrahydrofuran)
Column 3 PL gels manufactured by Polymer Laboratories
Column temperature 35 ° C
Liquid flow rate 0.7ml / min
Sample concentration 0.1% by weight
Sample injection volume 0.1ml
Detector Shodex RI SE-61 manufactured by Showa Denko KK
[0054]
[Microstructure]
It measured by the Hampton method [Analytical Chemistry, 21,923 (1949)] using the infrared spectrophotometer (FT-IR1650 by Perkin Elmer).
[Bound styrene content]
Measurement was carried out by a conventional method using an ultraviolet spectrophotometer (Hitachi UV200).
[Block styrene content]
The rubbery polymer composition is decomposed by oxidative decomposition with t-butyl hydroperoxide using osmium tetroxide as a catalyst [IMKolthoff, et.al., J. Poym. Sci. 1,429 (1946)]. The amount of the polystyrene component obtained was measured using an ultraviolet spectrophotometer (Hitachi UV200) and expressed as% by weight relative to the rubber-like polymer before decomposition.
[0055]
[Weight average molecular weight of block styrene part]
Polystyrene obtained by oxidative decomposition (IMKolthoff, et.al., J. Poym. Sci. 1, 429 (1946)) with t-butyl hydroperoxide using osmium tetroxide as a catalyst for rubbery polymers It is the molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
(GPC measurement conditions)
LC Model 1 manufactured by Waters
Solvent THF (tetrahydrofuran)
Column 3 PL gels manufactured by Polymer Laboratories
Column temperature 35 ° C
Liquid flow rate 0.7ml / min
Sample concentration 0.1% by weight
Sample injection volume 0.1ml
Detector Shodex RI SE-61 manufactured by Showa Denko KK
[0056]
[Izod impact strength]
The obtained composition was compression molded to prepare a test piece having a thickness of 3.2 mm, and measured according to JIS-K-7110.
[Glossy]
According to ASTM D-638, the glossiness (incident angle 60 °) of the gate portion and the end portion was measured and averaged.
[Rubber particle diameter]
An electron micrograph of the obtained resin by an ultrathin section method is taken, and the particle diameter of 300 to 600 rubber particles in the photograph is measured and weight averaged. That is, average rubber particle size = ΣniDi ^Four / ΣniDi ^Three (Ni is the number of rubber particles having a particle diameter Di).
[0057]
[Production of styrene-butadiene block copolymer (I)]
(1) An autoclave with an internal volume of 10 l and a jacketed autoclave was washed and dried, purged with nitrogen, and then purified and dried in advance under the conditions shown in Table 1, 1,3-butadiene and styrene, cyclohexane, 1,2-vinyl. Tetrahydrofuran or N, N, N ′, N′-tetramethylethylenediamine was added as a regulator, and then n-butyllithium was added to initiate polymerization. After completion of the reaction, butadiene was subsequently added, and polymerization was further continued. After completion of the polymerization, methanol was added to completely deactivate the living polymer. As a stabilizer, 0.56 parts by weight of 2,6-di-tert-butyl-4-methylphenol per 100 parts by weight of the polymer was added to the polymer solution thus obtained, and the solvent was removed by steam stripping. Drying was performed with a hot roll (110 ° C.) to obtain block copolymer (I) styrene-butadiene block copolymers of sample names (1) to (4) shown in Table 4.
[0058]
(2) An autoclave with an internal volume of 10 l and a jacketed autoclave was washed and dried, purged with nitrogen, and then purified and dried in advance under the conditions shown in Table 1, 1,3-butadiene, styrene and cyclohexane, 1,2-vinyl. Tetrahydrofuran was added as a regulator, and then n-butyllithium was added to initiate polymerization. After completion of the polymerization, styrene was subsequently added to continue the polymerization. After the polymerization was completed, butadiene was further added, and the polymerization was further continued. After completion of the polymerization, methanol was added to completely deactivate the living polymer. As a stabilizer, 0.56 parts by weight of 2,6-di-tert-butyl-4-methylphenol per 100 parts by weight of the polymer was added to the polymer solution thus obtained, and the solvent was removed by steam stripping. It was dried by a hot roll (110 ° C.) to obtain a block copolymer (I) styrene-butadiene block copolymer of sample name (5) shown in Table 4.
[0059]
(3) Washing and drying an agitator with an internal volume of 10 l and a jacketed autoclave, substituting with nitrogen, and purifying and drying in advance under the conditions shown in Table 1, 1,3-butadiene and styrene, cyclohexane, 1,2-vinyl Tetrahydrofuran was added as a regulator, and then n-butyllithium was added to initiate polymerization. After completion of the polymerization, styrene and butadiene were subsequently added to continue the polymerization. After completion of the polymerization, methanol was added to completely deactivate the living polymer. As a stabilizer, 0.56 parts by weight of 2,6-di-tert-butyl-4-methylphenol per 100 parts by weight of the polymer was added to the polymer solution thus obtained, and the solvent was removed by steam stripping. Drying was performed with a hot roll (110 ° C.) to obtain block copolymer (I) styrene-butadiene block copolymers of sample names (6), (7) and (8) shown in Table 4.
[0060]
(4) An autoclave with an internal volume of 10 liters and a jacketed autoclave was washed and dried, purged with nitrogen, then purified and dried in advance under the conditions shown in Table 1, 1,3-butadiene, cyclohexane, 1,2-vinyl adjuster Was added as tetrahydrofuran, and then n-butyllithium was added to initiate polymerization. After completion of the polymerization, styrene was subsequently added to continue the polymerization. After the polymerization was completed, butadiene was further added, and the polymerization was further continued. After completion of the polymerization, methanol was added to completely deactivate the living polymer. As a stabilizer, 0.56 parts by weight of 2,6-di-tert-butyl-4-methylphenol per 100 parts by weight of the polymer was added to the polymer solution thus obtained, and the solvent was removed by steam stripping. Drying was performed with a hot roll (110 ° C.) to obtain a block copolymer (I) styrene-butadiene block copolymer of sample name (9) shown in Table 4.
As described above, AS (styrene content in block A) and CS (styrene content in block C) in the styrene-butadiene block copolymer obtained in (1) to (4) are initial monomers (butadiene / styrene). It calculated | required by calculating from the styrene content of the rubber-like polymer composition after completion | finish of polymerization, and a block styrene content.
[0061]
[Production of styrene-butadiene block copolymer (II)]
(1) An autoclave with an internal volume of 10 liters and a jacketed autoclave was washed and dried, purged with nitrogen, then purified and dried in advance under the conditions shown in Table 2 and 1,3-butadiene and styrene, cyclohexane, 1,2-vinyl. Tetrahydrofuran or N, N, N ′, N′-tetramethylethylenediamine was added as a regulator, and then n-butyllithium was added to initiate polymerization. After completion of the polymerization, methanol was added to completely deactivate the living polymer. As a stabilizer, 0.56 parts by weight of 2,6-di-tert-butyl-4-methylphenol per 100 parts by weight of the polymer was added to the polymer solution thus obtained, and the solvent was removed by steam stripping. The styrene-butadiene block copolymer of block copolymer (II) samples A, B, and D shown in Table 5 was obtained by drying with a hot roll (110 ° C.).
[0062]
(2) Washing and drying an agitator with an internal volume of 10 l and a jacketed autoclave, substituting with nitrogen, and purifying and drying in advance under the conditions shown in Table 2, 1,3-butadiene and cyclohexane, 1,2-vinyl adjuster Then, tetrahydrofuran or N, N, N ′, N′-tetramethylethylenediamine was added, and then n-butyllithium was added to initiate polymerization. After completion of the polymerization, styrene was subsequently added, and the polymerization was further continued. After completion of the polymerization, methanol was added to completely deactivate the living polymer. 0.56 parts by weight of 2,6-di-tert-butyl-4-methylphenol per 100 parts by weight of the polymer was added as a stabilizer to the polymer solution thus obtained, and the solvent was removed by steam stripping. After dehydration, Subsequently, it was dried by a hot roll (110 ° C.) to obtain a block copolymer (II) sample C styrene-butadiene block copolymer shown in Table 5.
[0063]
[Production of rubber-like polymer composition]
(1) An autoclave with an internal volume of 10 l and a jacketed autoclave was washed and dried, purged with nitrogen, then purified and dried in advance under the conditions shown in Table 3 and 1,3-butadiene and styrene, cyclohexane, 1,2-vinyl. Tetrahydrofuran or N, N, N ′, N′-tetramethylethylenediamine was added as a regulator, and then n-butyllithium was added to initiate polymerization. After completion of the reaction, methanol was added to deactivate a part of the living polymer. Thereafter, butadiene was further added, and polymerization was continued. After completion of the polymerization, methanol was added to completely deactivate the living polymer. 0.56 parts by weight of 2,6-di-tert-butyl-4-methylphenol per 100 parts by weight of the polymer was added as a stabilizer to the polymer solution thus obtained, and the solvent was removed by steam stripping. After dehydration, Subsequently, it was dried by a hot roll (110 ° C.), and rubbery polymer compositions (1) -A and (2) -B of the block copolymer (I) and the block copolymer (II) shown in Table 6 were prepared. Obtained.
The properties of the block copolymer (I) and the block copolymer (II) were analyzed by separating the respective copolymers with a GPC column. Moreover, the weight ratio of each component was calculated | required from the area ratio of the molecular weight distribution curve of GPC.
[0064]
[Table 1]

[0065]
[Table 2]

[0066]
[Table 3]

[0067]
[Table 4]

[0068]
[Table 5]

[0069]
[Table 6]

[0070]
(Examples 1 to 10)
Production of impact-resistant styrene resin composition
Using various polymers shown in Tables 4 to 6, an impact-resistant styrene resin composition was obtained by the bulk polymerization method described below.
Ethylbenzene and styrene were added to a stirrer and a jacketed reactor in the types and proportions as shown in Table 7, and then as block copolymers and stabilizers shown in Tables 4 to 6, n-octadecyl-3- (3 ′ , 5'-di-tert-butyl-4'-hydroxyphenyl) propionate (0.3 parts by weight) and t-dodecyl mercaptan (0.05 parts by weight) were added and dissolved by stirring.
To this, 1 x 10 g of tert-butyl peroxide was added to 1 mol of monomer. ^-Four Mole was added and polymerization was performed at 110 ° C. for 3 hours, 140 ° C. for 5 hours, and 180 ° C. for 2 hours. Further, after heating at 230 ° C. for 30 minutes, the unreacted product was removed under reduced pressure, and the resulting polymer was pulverized and pelletized with an extruder. Table 7 shows the physical properties of the resulting impact-resistant styrenic resin composition. As is clear from the results of the examples, it can be seen that the impact-resistant styrenic resin composition produced using the polymer of the present invention has an excellent balance between gloss and impact strength.
[0071]
(Example 11)
Production of ABS resin
Using the same reactor as in Example 1, ethylbenzene, styrene, and acrylonitrile were added in the types and proportions shown in Table 7, and then n-octadecyl-3- (3 ^' , 5 ^' GE tert-butyl-4 ^' 0.3 parts by weight of (hydroxyphenyl) propionate and 0.05 parts by weight of t-dodecyl mercaptan were added and dissolved by stirring.
To this, 1 x 10 g of tert-butyl peroxide was added to 1 mol of monomer. ^-Four Mole was added and polymerization was performed at 110 ° C. for 3 hours, 140 ° C. for 5 hours, and 180 ° C. for 2 hours. Further, after heating at 230 ° C. for 30 minutes, the unreacted product was removed under reduced pressure, and the resulting polymer was pulverized and pelletized with an extruder to obtain an ABS resin.
Table 7 shows the physical properties of the ABS resin composition obtained. It can be seen that the ABS resin produced using the styrene-butadiene block copolymer of the invention has a small rubber particle size and an excellent balance between gloss and impact strength.
[0072]
(Example 12)
Manufacture of MBS resin
Using the same reactor as in Example 1, ethylbenzene, styrene and methyl methacrylate were added in the types and proportions shown in Table 7, followed by n-octadecyl-3- (3 ′, 5′-ji as rubber and stabilizer. tert-Butyl-4′-hydroxyphenyl) propionate (0.3 parts by weight) and t-dodecyl mercaptan (0.05 parts by weight) were added and dissolved by stirring.
To this, 1 x 10 g of tert-butyl peroxide was added to 1 mol of monomer. ^-Four Mole was added and polymerization was performed at 110 ° C. for 3 hours, 140 ° C. for 5 hours, and 180 ° C. for 2 hours. Furthermore, after heating at 230 ° C. for 30 minutes, the unreacted product was removed under reduced pressure, and the obtained polymer was pulverized and pelletized with an extruder to obtain an MBS resin.
[0073]
(Comparative Examples 1, 2, 3)
Manufacture of impact-resistant styrenic resin composition
Using various polymers shown in Table 8, an impact-resistant styrenic resin composition was obtained in the same manner as in Example 1.
Table 8 shows the physical properties of the resulting impact-resistant styrenic resin composition. When a rubbery polymer composition outside the scope of the present invention was used, impact strength or gloss was inferior, and an impact-resistant styrenic resin composition excellent in both was not obtained.
[0074]
[Table 7]

[0075]
[Table 8]

[0076]
【The invention's effect】
The rubbery polymer composition having a specific structure of the present invention has an unprecedented structure, and particularly when used as a toughening agent for an impact-resistant styrene resin composition, the conventional impact-resistant styrene. Compared with resin-based resin compositions, it is possible to obtain a material that is remarkably excellent in the balance of physical properties between impact resistance and gloss, such as electronic devices such as TVs and VTRs, home appliances such as air conditioners and refrigerators, OA office equipment It has an industrially excellent effect that it can be used for a wide variety of applications such as equipment, stationery, toys, leisure sports goods, household goods, building materials / housing parts, and food containers.

Claims (2)

The following general formula,
Block copolymer (I): A1-B1-C
Block copolymer (II): A2-B2
(Wherein, block A1 is a random copolymer comprising a conjugated diene monomer and aromatic vinyl monomer, block B1 is a polymer comprising an aromatic vinyl monomer, block C of the conjugated diene-based monomer Polymer consisting of a monomer or random copolymer consisting of a conjugated diene monomer and an aromatic vinyl monomer, block A2 is a polymer consisting of a conjugated diene monomer or a conjugated diene monomer and an aromatic Random copolymer consisting of an aromatic vinyl monomer, block B2 is a polymer consisting of an aromatic vinyl monomer.)
A rubbery polymer composition comprising 50 to 99 parts by weight of a block copolymer (I) represented by: 1 to 50 parts by weight of a block copolymer (II),
(1) Polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatograph of block copolymer (I) is 100,000 to 700,000.
(2) The total aromatic vinyl monomer content (TS) in the block copolymer (I) is 5 to 60% by weight,
(3) The content of aromatic vinyl monomer (BS) in the block copolymer (I) is 5 to 50% by weight,
(4) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the aromatic vinyl polymer that is the block in the block copolymer (I) is 5,000 to 150,000. ,
(A) Polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatograph of block copolymer (II) is 5 to 350,000,
(B) The total aromatic vinyl monomer content (TS) in the block copolymer (II) is 25 to 70% by weight,
(C) Aromatic vinyl monomer content (BS) which is a block in the block copolymer (II) is 5 to 70% by weight,
(D) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the aromatic vinyl polymer that is the block in the block copolymer (II) is 5,000 to 150,000. ,
A rubbery polymer composition characterized by the above. (A) 75 to 98 parts by weight of a mixture of an aromatic vinyl monomer or a monomer mainly composed of a monomer copolymerizable with the aromatic vinyl monomer,
(B) A rubber-modified impact-resistant resin composition obtained by radical polymerization of 2 to 25 parts by weight of a rubber-like polymer by a bulk polymerization method, a bulk suspension polymerization method or a solution polymerization method, The coalescence is the following general formula:
Block copolymer (I): A1-B1-C
Block copolymer (II): A2-B2
(Wherein, block A1 is a random copolymer comprising a conjugated diene monomer and aromatic vinyl monomer, block B1 is a polymer comprising an aromatic vinyl monomer, block C of the conjugated diene-based monomer Polymer consisting of a monomer or random copolymer consisting of a conjugated diene monomer and an aromatic vinyl monomer, block A2 is a polymer consisting of a conjugated diene monomer or a conjugated diene monomer and an aromatic Random copolymer consisting of an aromatic vinyl monomer, block B2 is a polymer consisting of an aromatic vinyl monomer.)
A rubbery polymer composition comprising 50 to 99 parts by weight of a block copolymer (I) represented by: 1 to 50 parts by weight of a block copolymer (II),
(1) Polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatograph of block copolymer (I) is 100,000 to 700,000.
(2) The total aromatic vinyl monomer content (TS) in the block copolymer (I) is 5 to 60% by weight,
(3) The content of aromatic vinyl monomer (BS) in the block copolymer (I) is 5 to 50% by weight,
(4) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the aromatic vinyl polymer that is the block in the block copolymer (I) is 5,000 to 150,000. ,
(A) Polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatograph of block copolymer (II) is 5 to 350,000,
(B) The total aromatic vinyl monomer content (TS) in the block copolymer (II) is 25 to 70% by weight,
(C) Aromatic vinyl monomer content (BS) which is a block in the block copolymer (II) is 5 to 70% by weight,
(D) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the aromatic vinyl polymer that is the block in the block copolymer (II) is 5,000 to 150,000. ,
A rubber-modified impact-resistant resin composition characterized by being a rubber-like polymer composition.