JP3628445B2 - Thermoplastic resin composition - Google Patents

Description

【００５８】
で表される粘度である。式中、η_ｓｐは比粘度、η_ｒ は相対粘度を示し、｛η_ｓｐ＝（η−η_０ ）／η_０ ＝η_ｒ −１｝により求められる。また、ｃは溶液の容積濃度（重量／容積）を示す。即ち、固有粘度は、濃度の異なる溶液の各粘度を測定し、それぞれの溶液の（η_ｓｐ／ｃ）あるいは（ｌｎη_ｒ ／ｃ）と容積濃度との関係において、適当な方法でｃを０に補外することによって求められる値を示す。
【００５９】
上記固有粘度を求める場合には、具体的には、共重合体（Ｙ）をジメチルホルムアミドに溶解させて、濃度の異なる溶液として、例えば濃度１ｇ／１００ｍｌ 、０．５ ｇ／１００ｍｌ 、０．３ ｇ／１００ｍｌ の３種の溶液を作製し、この溶液を３０℃に調製した後、ウベローデ粘度計により粘度を測定し、濃度を０に補外することによって求めることができる。
【００６０】
上記共重合体（Ｙ）の固有粘度は、０．１ 〜０．３５の範囲内となるように設計することが好ましい。上記共重合体（Ｙ）の固有粘度が上記の範囲内にあることで、得られる樹脂組成物（Ｉ）の流動性の低下を抑えることができると共に、耐熱性や耐溶剤性、加工性等の物性を低下させることなく、耐衝撃性を充分に向上させることができる。これにより、耐衝撃性に優れると共に、耐熱性、耐溶剤性、および加工性等の物性と耐衝撃性とのバランスのとれた樹脂組成物（Ｉ）を得ることができる。
【００６１】
一方、上記共重合体（Ｙ）の固有粘度が ０．１より小さいか、あるいは、０．３５より大きければ、上記樹脂組成物（Ｉ）の耐衝撃性を充分に向上させることは困難であり、また、耐衝撃性を向上させるために必要とする共重合体（Ｙ）の添加量が多くなる。さらに、上記樹脂組成物（Ｉ）の流動性の低下を引き起こすと共に、耐熱性、耐溶剤性、および加工性等の物性と耐衝撃性とのバランスが悪くなるので好ましくない。
【００６２】
上記共重合体（Ｙ）における、重量平均分子量／数平均分子量で定義される分子量分布が３以下となるように設計することが好ましい。上記共重合体（Ｙ）の分子量分布が上記の範囲内にあることで、得られる樹脂組成物（Ｉ）の流動性の低下を抑えることができると共に、耐熱性や耐溶剤性、加工性等の物性を低下させることなく、耐衝撃性を充分に向上させることができる。これにより、耐衝撃性に優れると共に、耐熱性、耐溶剤性、および加工性等の物性と耐衝撃性とのバランスのとれた樹脂組成物（Ｉ）を得ることができる。
【００６３】
一方、上記共重合体（Ｙ）の分子量分布が３を越えると、上記樹脂組成物（Ｉ）の耐衝撃性を充分に向上させることは困難であり、また、耐衝撃性を向上させるために必要とする共重合体（Ｙ）の添加量が多くなる。さらに、上記樹脂組成物（Ｉ）の流動性の低下を引き起こすと共に、耐熱性、耐溶剤性、および加工性等の物性と耐衝撃性とのバランスが悪くなるので好ましくない。
【００６４】
本発明にかかる樹脂組成物（Ｉ）は、上記ゴム強化スチレン系樹脂（Ａ）と、ポリマー（Ｘ）と、共重合体（Ｙ）とを混合することによって、容易に得ることができる。
【００６５】
上記ゴム強化スチレン系樹脂（Ａ）とポリマー（Ｘ）との配合割合は、特に限定されるものではないが、ポリマー（Ｘ）を９０重量部〜１０重量部に対して、ゴム強化スチレン系樹脂（Ａ）を１０重量部〜９０重量部の割合で配合することが好ましい。
【００６６】
上記ゴム強化スチレン系樹脂（Ａ）の配合割合が、１０重量部より少なければ、得られる樹脂組成物（Ｉ）が、耐衝撃性や加工性等の物性を充分に発揮することができないので好ましくない。一方、上記ゴム強化スチレン系樹脂（Ａ）の配合割合が９０重量部より多ければ、上記樹脂組成物（Ｉ）が、耐熱性や耐溶剤性等の物性を充分に発揮することができないので好ましくない。
【００６７】
また、上記ゴム強化スチレン系樹脂（Ａ）とポリマー（Ｘ）と共重合体（Ｙ）との合計量に対する上記共重合体（Ｙ）が有する反応基の量は、０を越えて0.05モル／kg以下であることが好ましい。
【００６８】
上記ゴム強化スチレン系樹脂（Ａ）とポリマー（Ｘ）と共重合体（Ｙ）との合計量に対する上記共重合体（Ｙ）が有する反応基の量が0.05モル／kgを越えると、得られる樹脂組成物（Ｉ）の耐熱性、耐溶剤性、および加工性等の物性が低下する虞れがあるので好ましくない。
【００６９】
上記ゴム強化スチレン系樹脂（Ａ）、ポリマー（Ｘ）、および共重合体（Ｙ）の混合方法は、特に限定されるものではなく、上記ゴム強化スチレン系樹脂（Ａ）、ポリマー（Ｘ）、および共重合体（Ｙ）を同時に混合してもよく、上記ゴム強化スチレン系樹脂（Ａ）、ポリマー（Ｘ）、および共重合体（Ｙ）のうち、予め２成分を混合した後、残る１成分を混合してもよい。また、上記ゴム強化スチレン系樹脂（Ａ）、ポリマー（Ｘ）、および共重合体（Ｙ）の混合順序も特に限定されるものではない。
【００７０】
さらに、混合時における上記各成分の状態は、特に限定されるものではなく、ペレット、ビーズ、パウダー等、種々の状態で混合することができる。上記各成分の混合には、具体的には、例えば、バンバリーミキサー等の高速攪拌機、ロール、１軸あるいは多軸の押出機等、従来公知の混練機を用いることができるが、特に限定されるものではない。
【００７１】
上記ポリマー（Ｘ）と共重合体（Ｙ）との組み合わせは、特に限定されるものではないが、上記ポリマー（Ｘ）がカルボキシル基を有するポリマーであり、共重合体（Ｙ）がオキサゾリン基および／またはエポキシ基を有する共重合体である組み合わせが、得られる樹脂組成物（Ｉ）の物性からみて特に好ましい。
【００７２】
また、本発明に係る熱可塑性樹脂組成物（以下、樹脂組成物（ＩＩ） と記す） は、ゴム強化スチレン系樹脂（Ａ）と、熱可塑性ポリエステル、ポリアミド、ポリカーボネートからなる群より選ばれる少なくとも一種のポリマー（以下、ポリマー（Ｗ）と記す）と、固有粘度が ０．１〜０．３５の範囲内であり、分子中に、オキサゾリン基および／またはエポキシ基を有する共重合体（以下、共重合体（Ｚ）と記す）とを含有してなる。
【００７３】
上記ゴム強化スチレン系樹脂（Ａ）としては、特に限定されるものではなく、前記例示の化合物と同様の化合物を用いることができる。上記ゴム強化スチレン系樹脂（Ａ）は、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００７４】
また、上記ポリマー（Ｗ）とは、熱可塑性ポリエステル、ポリアミド、ポリカーボネートからなる群より選ばれる少なくとも一種のポリマーである。上記熱可塑性ポリエステル、ポリアミド、およびポリカーボネートとしては、特に限定されるものではなく、前記ポリマー（Ｘ）において例示した化合物に相当する、同様の化合物を用いることができる。これらポリマー（Ｗ）は、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００７５】
また、上記共重合体（Ｚ）は、固有粘度が ０．１〜０．３５の範囲内であり、分子中に、オキサゾリン基および／またはエポキシ基を有する共重合体である。
【００７６】
上記共重合体（Ｚ）は、上記オキサゾリン基またはエポキシ基を有する重合性モノマーを、互いに、あるいは、該重合性モノマーと共重合可能なビニル系単量体と共重合させることによって容易に得ることができる。
【００７７】
上記オキサゾリン基を有する重合性モノマーおよびエポキシ基を有する重合性モノマーとしては、特に限定されるものではなく、前記共重合体（Ｙ）において例示した化合物に相当する、同様の化合物を用いることができる。上記各重合性モノマーは、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００７８】
また、上記各重合性モノマーと共重合可能なビニル系単量体としては、特に限定されるものではなく、前記共重合体（Ｙ）の製造方法において例示した化合物と同様の化合物を用いることができる。上記ビニル系単量体は、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００７９】
尚、上記共重合体（Ｚ）の製造方法としては、特に限定されるものではなく、前記共重合体（Ｙ）において例示した製造方法と同様の製造方法並びに製造条件を用いることができる。
【００８０】
上記共重合体（Ｚ）の固有粘度は、 ０．１〜０．３５の範囲内となるように設計することが好ましい。上記共重合体（Ｚ）の固有粘度が上記の範囲内にあることで、得られる樹脂組成物（ＩＩ） の流動性の低下を抑えることができると共に、耐熱性や耐溶剤性、加工性等の物性を低下させることなく、耐衝撃性を充分に向上させることができる。これにより、耐衝撃性に優れると共に、耐熱性、耐溶剤性、および加工性等の物性と、耐衝撃性とのバランスのとれた樹脂組成物（ＩＩ） を得ることができる。
【００８１】
一方、上記共重合体（Ｚ）の固有粘度が０．１ より小さいか、あるいは、０．３５より大きければ、上記樹脂組成物（ＩＩ） の耐衝撃性を充分に向上させることは困難であり、また、耐衝撃性を向上させるために必要とする共重合体（Ｚ）の添加量が多くなる。さらに、上記樹脂組成物（ＩＩ）の流動性の低下を引き起こすと共に、耐熱性、耐溶剤性、および加工性等の物性と耐衝撃性とのバランスが悪くなるので好ましくない。
【００８２】
本発明にかかる樹脂組成物（ＩＩ）は、上記ゴム強化スチレン系樹脂（Ａ）と、ポリマー（Ｗ）と、共重合体（Ｚ）とを混合することによって、容易に得ることができる。
【００８３】
上記ゴム強化スチレン系樹脂（Ａ）とポリマー（Ｗ）との配合割合は、特に限定されるものではないが、ポリマー（Ｗ）を９０重量部〜１０重量部に対して、ゴム強化スチレン系樹脂（Ａ）を１０重量部〜９０重量部の割合で配合することが好ましい。
【００８４】
上記ゴム強化スチレン系樹脂（Ａ）の配合割合が、１０重量部より少なければ、得られる樹脂組成物（ＩＩ）が、耐衝撃性や加工性等の物性を充分に発揮することができないので好ましくない。一方、上記ゴム強化スチレン系樹脂（Ａ）の配合割合が９０重量部より多ければ、上記樹脂組成物（ＩＩ）が、耐熱性や耐溶剤性等の物性を充分に発揮することができないので好ましくない。
【００８５】
また、上記ゴム強化スチレン系樹脂（Ａ）とポリマー（Ｗ）と共重合体（Ｚ）との合計量に対する上記共重合体（Ｚ）が有する反応基の量は、０を越えて0.05モル／kg以下であることが好ましい。
【００８６】
上記ゴム強化スチレン系樹脂（Ａ）とポリマー（Ｗ）と共重合体（Ｚ）との合計量に対する上記共重合体（Ｚ）が有する反応基の量が0.05モル／kgを越えると、得られる樹脂組成物（II）の耐熱性、耐溶剤性、および加工性等の物性が低下する虞れがあるので好ましくない。
【００８７】
上記ゴム強化スチレン系樹脂（Ａ）、ポリマー（Ｗ）、および共重合体（Ｚ）の混合方法並びに混合時における上記各成分の状態は、前記樹脂組成物（Ｉ）の場合と同様、特に限定されるものではない。
【００８８】
本発明にかかる熱可塑性樹脂組成物（以下、樹脂組成物(III) と称する）は、ゴム強化スチレン系樹脂（Ａ）と、結晶性ポリマー（以下、ポリマー（Ｂ）と記す）と、固有粘度が 0.1〜0.35の範囲内であり、分子中に、オキサゾリン基、エポキシ基、酸無水物基、イソシアネート基からなる群より選ばれる少なくとも一種の反応基を含む共重合体（以下、共重合体（Ｃ）と記す）とを含有してなる。
【００８９】
上記ゴム強化スチレン系樹脂（Ａ）としては、特に限定されるものではなく、前記例示の化合物と同様の化合物を用いることができる。上記ゴム強化スチレン系樹脂（Ａ）は、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００９０】
また、上記ポリマー（Ｂ）としては、具体的には、例えば、熱可塑性ポリエステル、ポリアミド、ポリアセタール、ポリオレフィン等が挙げられるが、結晶性の熱可塑性樹脂であれば、特に限定されるものではない。これら結晶性ポリマー（Ｂ）は、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００９１】
上記熱可塑性ポリエステルとしては、特に限定されるものではなく、前記ポリマー（Ｘ）において例示した化合物と同様の化合物を用いることができる。上記熱可塑性ポリエステルは、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００９２】
上記ポリアミドとしては、特に限定されるものではなく、前記ポリマー（Ｘ）において例示した化合物と同様の化合物を用いることができる。上記ポリアミドは、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００９３】
上記ポリアセタールとは、ホルムアルデヒドを重合し、高分子量化したものであり、具体的には、例えば、ジュラコン（商品名：ポリプラスチック株式会社製）、テナック（旭化成工業株式会社製）、ユピナール（三菱瓦斯化学株式会社製）等が挙げられるが、特に限定されるものではない。これらポリアセタールは、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００９４】
上記ポリオレフィンとしては、具体的には、例えば、ポリエチレン、ポリプロピレン等が挙げられるが、特に限定されるものではない。これらポリオレフィンは、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００９５】
また、上記共重合体（Ｃ）は、固有粘度が 0.1〜0.35の範囲内であり、分子中に、オキサゾリン基、エポキシ基、酸無水物基、イソシアネート基からなる群より選ばれる少なくとも一種の反応基を有する共重合体である。
【００９６】
上記共重合体（Ｃ）は、オキサゾリン基、エポキシ基、酸無水物基、イソシアネート基からなる群より選ばれる反応基を有する重合性モノマーを、互いに、あるいは、該重合性モノマーと共重合可能な他のビニル系単量体と共重合させることによって容易に得ることができる。
【００９７】
上記オキサゾリン基を有する重合性モノマー、エポキシ基を有する重合性モノマー、酸無水物基を有する重合性モノマー、およびイソシアネート基を有する重合性モノマーとしては、前記共重合体（Ｙ）において例示した化合物に相当する、同様の化合物を用いることができる。これら重合性モノマーは、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００９８】
また、上記各重合性モノマーと共重合可能なビニル系単量体としては、特に限定されるものではなく、前記共重合体（Ｙ）の製造方法において例示した化合物と同様の化合物を用いることができる。上記ビニル系単量体は、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。
【００９９】
また、上記共重合体（Ｃ）の製造方法としては、特に限定されるものではなく、前記共重合体（Ｙ）において例示した製造方法と同様の製造方法並びに製造条件を用いることができる。
【０１００】
上記共重合体（Ｃ）の固有粘度は、 ０．１〜０．３５の範囲内となるように設計することが好ましい。上記共重合体（Ｃ）の固有粘度が上記の範囲内にあることで、得られる樹脂組成物（ＩＩＩ）の流動性の低下を抑えることができると共に、耐熱性や耐溶剤性、加工性等の物性を低下させることなく、耐衝撃性を充分に向上させることができる。これにより、耐衝撃性に優れると共に、耐熱性、耐溶剤性、および加工性等の物性と、耐衝撃性とのバランスのとれた樹脂組成物（ＩＩＩ）を得ることができる。
【０１０１】
一方、上記共重合体（Ｃ）の固有粘度が ０．１より小さいか、あるいは、０．３５より大きければ、上記樹脂組成物（ＩＩＩ）の耐衝撃性を充分に向上させることは困難であり、また、耐衝撃性を向上させるために必要とする共重合体（Ｃ）の添加量が多くなる。さらに、上記樹脂組成物（ＩＩＩ）の流動性の低下を引き起こすと共に、耐熱性、耐溶剤性、および加工性等の物性と耐衝撃性とのバランスが悪くなるので好ましくない。
【０１０２】
本発明にかかる樹脂組成物（ＩＩＩ） は、上記ゴム強化スチレン系樹脂（Ａ）と、ポリマー（Ｂ）と、共重合体（Ｃ）とを混合することによって、容易に得ることができる。
【０１０３】
上記ゴム強化スチレン系樹脂（Ａ）とポリマー（Ｂ）との配合割合は、特に限定されるものではないが、ポリマー（Ｂ）を９０重量部〜１０重量部に対して、ゴム強化スチレン系樹脂（Ａ）を１０重量部〜９０重量部の割合で配合することが好ましい。
【０１０４】
上記ゴム強化スチレン系樹脂（Ａ）の配合割合が、１０重量部より少なければ、得られる樹脂組成物（ＩＩＩ） が、耐衝撃性や加工性等の物性を充分に発揮することができないので好ましくない。一方、上記ゴム強化スチレン系樹脂（Ａ）の配合割合が９０重量部より多ければ、得られる樹脂組成物（ＩＩＩ） が、耐熱性や耐薬品性等の物性を充分に発揮することができないので好ましくない。
【０１０５】
また、上記ゴム強化スチレン系樹脂（Ａ）とポリマー（Ｂ）と共重合体（Ｃ）との合計量に対する上記共重合体（Ｃ）が有する反応基の量は、０を越えて0.05モル／kg以下であることが好ましい。
【０１０６】
上記ゴム強化スチレン系樹脂（Ａ）とポリマー（Ｂ）と共重合体（Ｃ）との合計量に対する上記共重合体（Ｃ）が有する反応基の量が0.05モル／kgを越えると、得られる樹脂組成物（III)の耐熱性、耐溶剤性、および加工性等の物性が低下する虞れがあるので好ましくない。
【０１０７】
上記ゴム強化スチレン系樹脂（Ａ）、ポリマー（Ｂ）、および共重合体（Ｃ）の混合方法並びに混合時における上記各成分の状態は、前記樹脂組成物（Ｉ）の場合と同様、特に限定されるものではない。
【０１０８】
また、上記各樹脂組成物（Ｉ）・ （ＩＩ） ・（ＩＩＩ） には、必要に応じて、顔料や染料、ガラス繊維、金属繊維、炭素繊維、金属フレーク等の補強材や充填材、酸化防止剤、紫外線吸収剤、光安定剤、熱安定剤、帯電防止剤、滑剤、可塑剤、難燃剤等の従来公知の種々の添加剤を添加してもよい。これら添加剤は、一種類のみを用いてもよいし、二種類以上を適宜混合して用いてもよい。また、これら添加剤の添加量は、特に限定されるものではない。
【０１０９】
また、所望する物性に応じて、上記各樹脂組成物（Ｉ）・ （ＩＩ） ・（ＩＩＩ） に、ポリアセタール、ポリメチルメタクリレート、塩化ビニル等の、他の熱可塑性樹脂を適宜配合してもよい。さらに、上記各樹脂組成物（Ｉ）・ （ＩＩ） ・（ＩＩＩ） は、各々単独で用いてもよいし、適宜混合して用いてもよい。
【０１１０】
以上のように、本発明に係る熱可塑性樹脂組成物は、上記ゴム強化スチレン系樹脂（Ａ）と各ポリマーとを相溶化させるための相溶化剤として、固有粘度が 0.1〜0.35の範囲内であり、分子中に、上記各ポリマーが有する官能基と反応する反応基を有する共重合体を含むことで、耐衝撃性を向上させるために必要とする相溶化剤の使用量を少ない量に（０を越えて0.05モル／kg以下）抑えることができる。
【０１１１】
さらに、本発明によれば、得られる各樹脂組成物（Ｉ）・ （ＩＩ） ・（ＩＩＩ）の流動性の低下を抑えることができると共に、耐熱性や耐溶剤性、加工性等の物性を低下させることなく、耐衝撃性を充分に向上させることができる。これにより、耐衝撃性に優れると共に、耐熱性、耐溶剤性、および加工性等の物性と、耐衝撃性とのバランスのとれた樹脂組成物を得ることができる。
【０１１２】
つまり、本発明にかかる各樹脂組成物（Ｉ）・ （ＩＩ） ・（ＩＩＩ）は、耐衝撃性に優れると共に、耐熱性、耐溶剤性、および加工性等の物性と耐衝撃性とのバランスに優れている。尚、上記加工性は、各樹脂組成物（Ｉ）・ （ＩＩ） ・（ＩＩＩ）の流動性により評価することができる。
【０１１３】
このため、上記各樹脂組成物（Ｉ）・ （ＩＩ） ・（ＩＩＩ）は、何れも、例えば、冷蔵庫、洗濯機、掃除機等の家庭電気器具、自動車の内外装部品、雑貨用、家具建材等、耐熱性、耐溶剤性、加工性、および耐衝撃性等の物性を必要とする広範な用途に利用することができる。
【０１１４】
【実施例】
以下、実施例および比較例により、本発明をさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。また、熱可塑性樹脂組成物の耐衝撃性、耐熱性、加工性、および分子量分布は以下の各方法によりそれぞれ評価された。
【０１１５】
耐衝撃性は、得られた樹脂組成物を成形して得られた試験片のいわゆる１／４’’ ノッチ付きアイゾット衝撃強度を測定することによって評価された。つまり、中央にＶ字形のノッチ（切込み）を入れた試験片を一端で支え、ノッチと同じ側からハンマーで打撃し、その破損によって吸収されたエネルギーの大きさを求められた。尚、上記耐衝撃性の測定は、ＪＩＳ Ｋ ７１１０に記載の２号試験片を用いて、ＪＩＳ Ｋ ７１１０に基づいて実施された。
【０１１６】
耐熱性は、得られた樹脂組成物を成形して得られた試験片の熱変形温度（荷重たわみ温度）を測定することによって評価された。つまり、試験片（１２．５ｍｍ×６ｍｍ）の中央部に１８．５ｋｇｆ／ｃｍ^２ の応力の相当する荷重を加え、２℃／ｍｉｎの速度で昇温させ、試験片に０．２６ｍｍのたわみを生ずる時の温度をもって、荷重たわみ温度とした。尚、上記耐熱性の測定は、ＪＩＳ Ｋ ７２０７に基づいて実施された。
【０１１７】
加工性は、得られた樹脂組成物の流動性を測定することによって評価した。つまり、得られた樹脂組成物を、温度２４０ ℃、荷重１０ｋｇの条件下で所定の試験装置から押し出し、１０分間あたりの押し出し量（ＭＦＲ）を求められた。つまり、ＭＦＲの値が大きいほど流動性が高いことを示す。尚、上記流動性の測定は、ＪＩＳ Ｋ ７２１０に基づいて実施された。
【０１１８】
また、共重合体の固有粘度は、以下の方法により求めた。先ず、得られた共重合体をジメチルホルムアミドに溶解させて、濃度１ｇ／１００ｍｌ 、０．５ ｇ／１００ｍｌ 、０．３ ｇ／１００ｍｌ の３種の溶液を作製した。次いで、この３種の溶液を３０℃に調製した後、ウベローデ粘度計によりその粘度を測定し、濃度を０に補外することによって求められた。
【０１１９】
分子量分布は、重量平均分子量をＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｏｈｙ）法に基づいて測定し、一方、数平均分子量もＧＰＣ法に基づき測定し、それらの結果から算出された。
【０１２０】
〔実施例１〕
先ず、還流管、温度センサー、ガス導入管、滴下装置および攪拌装置を取り付けた反応容器を窒素ガスで充分に置換した。次いで、この反応容器に、溶媒としてのトルエン１００ 部、および、連鎖移動剤としてのα−メチルスチレンダイマー１部を仕込んだ。一方、滴下装置に、芳香族ビニル系単量体であるスチレン７０部と、他のビニル系単量体であるアクリロニトリル２５部と、オキサゾリン基を有する重合性モノマーである２−イソプロペニル−２−オキサゾリン５部との混合物並びに重合開始剤としてのｔ−ブチルパーオキシ−２−エチルヘキサノエート２部を仕込んだ。
【０１２１】
次に、上記の反応溶液を１００ ℃に昇温した後、攪拌下で、滴下装置内の上記混合物および重合開始剤を４時間かけて徐々に該反応溶液に滴下した。
【０１２２】
滴下終了後、上記の反応溶液をさらに３時間攪拌することにより反応を完了させた。その結果、淡黄色の粘稠なポリマー溶液を得た。次いで、このポリマー溶液を、所定の方法により減圧脱揮し、ペレット化することにより、オキサゾリン基変性共重合体（以下、共重合体（ａ）と記す）を得た。ジメチルホルムアミドを溶媒として測定した３０℃における上記共重合体（ａ）の固有粘度は、０．２７であり、上記共重合体（ａ）の分子量分布は、２．３ であった。
【０１２３】
次いで、ゴム強化系スチレン樹脂（Ａ）としての市販のＡＢＳ樹脂（日本合成ゴム株式会社製、商品名：ＡＢＳ＃１０；以下、ＡＢＳと記す）５０部、エンジニアリングプラスチックとしての市販のポリブチレンテレフタレート（三菱エンジニアリングプラスチック株式会社製の飽和ポリエステル樹脂、商品名：ノバドール５０１０；以下、ＰＢＴと記す）５０部、および上記共重合体（ａ）３部を混合して、２軸押出機で溶融混合することによってペレット状の樹脂組成物（以下、樹脂組成物（１）と記す）を得た。
【０１２４】
上記共重合体（ａ）３部は、オキサゾリン基の含有量に換算すると、０．０１３５モル／ｋｇに相当する。また、上記樹脂組成物（１）について、上述した方法により流動性を測定した。
【０１２５】
その後、上記樹脂組成物（１）から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を上述した方法により測定した。上記ＡＢＳ、ＰＢＴ、および共重合体（ａ）の混合条件と、各試験結果とをまとめて表１に示す。
【０１２６】
【表１】

【０１２７】
〔実施例２〕
実施例１において、上記共重合体（ａ）の添加量を３部から５部に変更した以外は、実施例１と同様の方法を用いてペレット状の樹脂組成物（以下、樹脂組成物（２）と記す）を得た。上記共重合体（ａ）５部は、オキサゾリン基の含有量に換算すると、０．０２２５モル／ｋｇに相当する。また、上記樹脂組成物（２）について、実施例１と同様の方法により流動性を測定した。
【０１２８】
その後、上記樹脂組成物（２）から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を実施例１と同様の方法により測定した。上記ＡＢＳ、ＰＢＴ、および共重合体（ａ）の混合条件と、各試験結果とをまとめて表１に示す。
【０１２９】
〔実施例３〕
実施例１において、α−メチルスチレンダイマーの量を１部から３部に変更した以外は、実施例１と同様の反応・操作を行って、オキサゾリン基変性共重合体（以下、共重合体（ｂ）と記す）を得た。ジメチルホルムアミドを溶媒として測定した３０℃における上記共重合体（ｂ）の固有粘度は、０．１６であり、上記共重合体（ｂ）の分子量分布は、２．１ であった。
【０１３０】
次いで、実施例１において、上記共重合体（ａ）の代わりに、共重合体（ｂ）３部を用いた以外は、実施例１と同様の方法を用いてペレット状の樹脂組成物（以下、樹脂組成物（３） と記す）を得た。上記共重合体（ｂ）３部は、オキサゾリン基の含有量に換算すると、０．０１３５モル／ｋｇに相当する。また、上記樹脂組成物（３）について、実施例１と同様の方法により流動性を測定した。
【０１３１】
その後、上記樹脂組成物（３） から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を実施例１と同様の方法により測定した。上記ＡＢＳ、ＰＢＴ、および共重合体（ｂ）の混合条件と、各試験結果とをまとめて表１に示す。
【０１３２】
〔実施例４〕
実施例３において、上記共重合体（ｂ）の添加量を３部から５部に変更した以外は、実施例３と同様の方法を用いてペレット状の樹脂組成物（以下、樹脂組成物（４）と記す）を得た。上記共重合体（ｂ）５部は、オキサゾリン基の含有量に換算すると、０．０２２５モル／ｋｇに相当する。また、上記樹脂組成物（４）について、実施例１と同様の方法により流動性を測定した。
【０１３３】
その後、上記樹脂組成物（４）から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を実施例３、即ち、実施例１と同様の方法により測定した。上記ＡＢＳ、ＰＢＴ、および共重合体（ｂ）の混合条件と、各試験結果とをまとめて表１に示す。
【０１３４】
〔比較例１〕
ＡＢＳ５０部およびＰＢＴ５０部を混合して、２軸押出機で溶融混合してペレット化することによって、ペレット状の比較用樹脂組成物（以下、樹脂組成物（５）と記す）を得た。また、上記樹脂組成物（５）について、実施例１と同様の方法により流動性を測定した。
【０１３５】
その後、上記樹脂組成物（５）から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を実施例１と同様の方法により測定した。上記ＡＢＳおよびＰＢＴの混合条件と、各試験結果とをまとめて表２に示す。
【０１３６】
【表２】

【０１３７】
〔比較例２〕
実施例１において、α−メチルスチレンダイマーを添加しなかった以外は、実施例１と同様の反応・操作を行って、比較用のオキサゾリン基変性共重合体（以下、共重合体（ｃ）と記す）を得た。ジメチルホルムアミドを溶媒として測定した３０℃における上記共重合体（ｃ）の固有粘度は、０．４４であり、上記共重合体（ｃ）の分子量分布は、２．３ であった。
【０１３８】
次いで、実施例１において、上記共重合体（ａ）の代わりに、共重合体（ｃ）３部を用いた以外は、実施例１と同様の方法を用いてペレット状の比較用樹脂組成物（以下、樹脂組成物（６）と記す）を得た。上記共重合体（ｃ）３部は、オキサゾリン基の含有量に換算すると、０．０１３５モル／ｋｇに相当する。また、上記樹脂組成物（６）について、実施例１と同様の方法により流動性を測定した。
【０１３９】
その後、上記樹脂組成物（６）から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を実施例１と同様の方法により測定した。上記ＡＢＳ、ＰＢＴ、および共重合体（ｃ）の混合条件と、各試験結果とをまとめて表２に示す。
【０１４０】
〔比較例３〕
比較例２において、上記共重合体（ｃ）の添加量を３部から５部に変更した以外は、比較例２と同様の方法を用いてペレット状の樹脂組成物（以下、樹脂組成物（７） と記す）を得た。上記共重合体（ｃ）５部は、オキサゾリン基の含有量に換算すると、０．０２２５モル／ｋｇに相当する。また、上記樹脂組成物（７）について、実施例１と同様の方法により流動性を測定した。
【０１４１】
その後、上記樹脂組成物（７） から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を比較例２、即ち、実施例１と同様の方法により測定した。上記ＡＢＳ、ＰＢＴ、および共重合体（ｃ）の混合条件と、各試験結果とをまとめて表２に示す。
【０１４２】
〔比較例４〕
実施例１において、α−メチルスチレンダイマーの量を１部から５部に変更した以外は、実施例１と同様の反応・操作を行って、比較用のオキサゾリン変性共重合体（以下、共重合体（ｄ）と記す）を得た。ジメチルホルムアミドを溶媒として測定した３０℃における上記共重合体（ｄ）の固有粘度は、０．０７であり、上記共重合体（ｄ）の分子量分布は、２．０ であった。
【０１４３】
次いで、実施例１において、上記共重合体（ａ）の代わりに、共重合体（ｄ）５部を用いた以外は、実施例１と同様の方法を用いてペレット状の比較用樹脂組成物（以下、樹脂組成物（８）と記す）を得た。上記共重合体（ｄ）５部は、オキサゾリン基の含有量に換算すると、０．０２２５モル／ｋｇに相当する。また、上記樹脂組成物（８）について、実施例１と同様の方法により流動性を測定した。
【０１４４】
その後、上記樹脂組成物（８）から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を実施例１と同様の方法により測定した。上記ＡＢＳ、ＰＢＴ、および共重合体（ｄ）の混合条件と、各試験結果とをまとめて表２に示す。
【０１４５】
〔実施例５〕
ゴム強化スチレン系樹脂（Ａ）としてのＡＢＳ５０部、エンジニアリングプラスチックとしての市販のポリカーボネート（帝人化成株式会社製、商品名：パンライトＬ−１２５０；以下、ＰＣと記す）５０部、および上記共重合体（ａ）５部を混合して、２軸押出機で溶融混合することによってペレット状の樹脂組成物（以下、樹脂組成物（９）と記す）を得た。また、上記樹脂組成物（９）について、実施例１と同様の方法により流動性を測定した。
【０１４６】
その後、上記樹脂組成物（９）から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を所定の方法により測定した。上記ＡＢＳ、ＰＣ、および共重合体（ａ）の混合条件と、各試験結果とをまとめて表１に示す。
【０１４７】
〔比較例５〕
実施例５において、共重合体（ａ）の代わりに、共重合体（ｃ）５部を用いた以外は、実施例５と同様の方法を用いてペレット状の比較用樹脂組成物（以下、樹脂組成物（１０）と記す）を得た。また、上記樹脂組成物（１０）について、実施例１と同様の方法により流動性を測定した。
【０１４８】
その後、上記樹脂組成物（１０）から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を実施例１と同様の方法により測定した。上記ＡＢＳ、ＰＣ、および共重合体（ｃ）の混合条件と、各試験結果とをまとめて表２に示す。
【０１４９】
〔比較例６〕
ＡＢＳ５０部およびＰＣ５０部を混合して、２軸押出機で溶融混合してペレット化することによって、ペレット状の比較用樹脂組成物（以下、樹脂組成物（１１）と記す）を得た。また、上記樹脂組成物（１１）について、実施例１と同様の方法により流動性を測定した。
【０１５０】
その後、上記樹脂組成物（１１）から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を実施例１と同様の方法により測定した。上記ＡＢＳおよびＰＣの混合条件と、各試験結果とをまとめて表２に示す。
【０１５１】
上記表１および表２に記載の結果から明らかなように、本実施例で得られた樹脂組成物（１）〜（４）は、耐熱性を低下させることなく、比較例で得られた樹脂組成物（５）〜（８）に比べて耐衝撃性が向上したものとなっている。また、本実施例で得られた樹脂組成物（９）は、耐熱性を低下させることなく、比較例で得られた樹脂組成物（１０）・（１１） に比べて耐衝撃性が向上したものとなっている。
【０１５２】
さらに、本実施例にて得られた各試験片について、耐溶剤性を目視により観察したところ、溶剤による試験片表面の劣化は、比較例の試験片表面の劣化と比べて明らかに改善されていた。
【０１５３】
〔実施例６〕
先ず、還流管、温度センサー、ガス導入管、滴下装置および攪拌装置を取り付けた反応容器を窒素ガスで充分に置換した。次いで、この反応容器に、溶媒としてのトルエン１００ 部、および、連鎖移動剤としてのα−メチルスチレンダイマー１部を仕込んだ。
【０１５４】
一方、滴下装置に、アクリロニトリル２４．７部、スチレン６９部、グリシジルメタクリレート ６．３部の混合物と、並びに重合開始剤としてのｔ−ブチルパーオキシ−２−エチルヘキサノエート２部を仕込んだ。
【０１５５】
次に、上記の反応容器内の溶液を１００ ℃に昇温した後、滴下装置内の上記混合物および重合開始剤を４時間かけて、激しく攪拌しながら、徐々に該反応溶液に滴下した。
【０１５６】
滴下終了後、上記の反応溶液をさらに３時間攪拌することにより熟成させて、反応を完了させた。その結果、淡黄色の粘稠なポリマー溶液を得た。次いで、このポリマー溶液を、所定の方法により減圧脱揮し、ペレット化することにより、エポキシ基変性共重合体（以下、共重合体（ｅ）と記す）を得た。ジメチルホルムアミドを溶媒として測定した３０℃における上記共重合体（ｅ）の固有粘度は、０．２７であり、上記共重合体（ｅ）の分子量分布は、 ２．２であった。
【０１５７】
次に、前記のＡＢＳ５０部、前記のＰＢＴ５０部、および上記共重合体（ｅ）５部を混合して、２軸押出機で溶融混合することによってペレット状の樹脂組成物（以下、樹脂組成物（１２）と記す）を得た。上記共重合体（ｅ）５部は、エポキシ基の含有量に換算すると、０．０２２５モル／ｋｇに相当する。また、上記樹脂組成物（１２）について、上述した方法により流動性を測定した。
【０１５８】
その後、上記樹脂組成物（１２）から射出成形機を用いて試験片を作成した。この試験片の耐衝撃性および耐熱性を上述した方法により測定した。上記ＡＢＳ、ＰＢＴ、および共重合体（ｅ）の混合条件と、各試験結果とをまとめて表１に示す。
【０１５９】
表１の結果から明らかなように、本発明の熱可塑性樹脂組成物では、エポキシ基変性の共重合体（ｅ）を用いても、オキサゾリン基変性の共重合体と同様に、耐熱性を維持しながら、耐衝撃性を改善できる。
【０１６０】
実施例１〜６の各樹脂組成物は、表１および表２の結果から明らかなように、耐熱性を低下させることなく、共重合体の分子量分布を２〜２．３ とすることによって、得られたアイゾット耐衝撃性が高いものであることが判る。
【０１６１】
このことから、本発明の熱可塑性樹脂組成物では、反応基を有する共重合体における分子量分布を３以下、さらに好ましくは２〜2.5 とすることによって、得られる熱可塑性樹脂組成物において、耐熱性を維持しながら、耐衝撃性をさらに向上させることが可能となる。
【０１６２】
【発明の効果】
本発明の熱可塑性樹脂組成物は、以上のように、ゴム強化スチレン系樹脂と、熱可塑性ポリエステル、ポリアミド、ポリカーボネートからなる群より選ばれる少なくとも一種のポリマーと、分子中に、オキサゾリン基を反応基として有する共重合体とを含有し、上記共重合体の固有粘度が０．１〜０．３５である構成である。
【０１６３】
また、上記熱可塑性樹脂組成物では、上記共重合体における、上記オキサゾリン基を有する重合性モノマーの配合量が、０．１重量％〜２０重量％の範囲内であってもよい。
【０１６４】
また、上記熱可塑性樹脂組成物においては、上記共重合体は、上記ポリマーの官能基と反応する反応基を有する重合性モノマーと、該重合性モノマーと共重合可能なビニル系単量体とを、固有粘度が０．１〜０．３５となるように、連鎖移動剤を上記固有粘度を調整するために用いて共重合させたものであってもよい。上記連鎖移動剤は、α−メチルスチレンダイマーであってもよい。
【０１６５】
また、本発明の熱可塑性樹脂組成物は、さらに、上記共重合体が有する反応基の量が、ゴム強化スチレン系樹脂とポリマーと共重合体との合計量に対して０を越えて0.05モル／kg以下である構成である。
【０１６６】
本発明の熱可塑性樹脂組成物は、さらに、上記共重合体における、重量平均分子量／数平均分子量で定義される分子量分布が３以下である構成である。
【０１６７】
上記の構成によれば、本発明にかかる熱可塑性樹脂組成物は、ゴム強化スチレン系樹脂といわゆるエンジニアリングプラスチックと呼ばれるポリマー（カルボキシル基、水酸基、アミノ基からなる群より選ばれる少なくとも一種の官能基を有するポリマーや、熱可塑性ポリエステル、ポリアミド、またはポリカーボネートからなる群より選ばれる少なくとも一種のポリマーや、結晶性ポリマー）とを相溶化させるための相溶化剤として、固有粘度が上記範囲内にある共重合体を含むことで、耐衝撃性を向上させるために必要とする相溶化剤の使用量を少なく（０を越えて０．０５モル／ｋｇ以下）抑えることができる。
【０１６８】
このため、上記の構成では、上記各樹脂組成物の流動性の低下を抑えることができると共に、耐熱性や耐溶剤性、加工性等の物性を低下させることなく、耐衝撃性を充分に向上させることができる。
【０１６９】
また、上記共重合体における、重量平均分子量／数平均分子量で定義される分子量分布が３以下とすることにより、さらに、上記各樹脂組成物の流動性の低下を抑えることができると共に、耐熱性や耐溶剤性、加工性等の物性を低下させることなく、耐衝撃性を充分に向上させることができる。
【０１７０】
これにより、上記構成では、耐衝撃性に優れると共に、耐熱性、耐溶剤性、および加工性等の物性と、耐衝撃性とのバランスのとれた熱可塑性樹脂組成物とすることができる。つまり、本発明にかかる熱可塑性樹脂組成物は、耐衝撃性に優れると共に、耐熱性、耐溶剤性、および加工性等の物性と耐衝撃性とのバランスに優れているという効果を併せて奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermoplastic resin containing a polymer called a so-called engineering plastic, a rubber-reinforced styrene resin, and a copolymer as a compatibilizer for compatibilizing the polymer and the rubber-reinforced styrene resin. It relates to a composition.
[0002]
[Prior art]
Conventionally, rubber-reinforced styrene resins such as ABS resin (acrylonitrile-butadiene-styrene copolymer) and impact-resistant styrene resin have excellent impact resistance and molding processability (hereinafter referred to as processability), As a general-purpose thermoplastic resin, it is used in a wide range of fields such as the automotive field and the electrical component field. However, the rubber-reinforced styrene-based resin has a problem in that physical properties such as heat resistance and chemical resistance are not sufficient and the usage is limited.
[0003]
On the other hand, as a polymer excellent in physical properties such as heat resistance and chemical resistance, a group of thermoplastic resins called engineering plastics mainly used as mechanical materials and various functional parts are known. However, the engineering plastic has a problem that it is excellent in physical properties such as heat resistance and chemical resistance, but is inferior in physical properties such as dimensional stability.
[0004]
Therefore, in order to improve the impact resistance of the engineering plastic, a method of mixing a rubber-reinforced styrene resin with the engineering plastic is generally used.
[0005]
However, simply mixing a rubber-reinforced styrene resin with the engineering plastic does not make them compatible with each other, and therefore, sufficient impact resistance cannot be obtained. Therefore, by adding a reactive polymer called a compatibilizer, the compatibility between the engineering plastic and the rubber-reinforced styrene resin is improved, thereby improving the impact resistance of the resulting thermoplastic resin. ing.
[0006]
As a thermoplastic resin composition using such a compatibilizing agent, for example, a thermoplastic resin composition described in JP-A-3-76747 is known.
[0007]
[Problems to be solved by the invention]
However, although the thermoplastic resin composition of the above publication is improved in impact resistance by adding the compatibilizing agent, it is still difficult to say that it has been sufficiently improved. Therefore, even if more compatibilizer is added in order to obtain a sufficient impact resistance modification effect, further improvement in impact resistance cannot be expected. Addition of a large amount of a compatibilizer causes a decrease in processability such as fluidity. That is, it is difficult to sufficiently improve workability and impact resistance.
[0008]
In general, attempts have been made to increase the content of functional groups in the compatibilizer for the purpose of reducing the amount of compatibilizer added. However, in this case, side reactions are likely to occur, and the fluidity of the entire thermoplastic resin composition is lowered. For this reason, there exists a problem that workability is impaired.
[0009]
Therefore, there is a demand for a thermoplastic resin composition that is excellent in impact resistance and excellent in balance between physical properties such as heat resistance, solvent resistance, and workability and impact resistance. Accordingly, an object of the present invention is to provide a thermoplastic resin composition that is excellent in impact resistance and excellent in balance between physical properties such as heat resistance, solvent resistance, and workability and impact resistance.
[0010]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned object, the inventors of the present application have a rubber-reinforced styrene resin, a polymer called engineering plastic, and an intrinsic viscosity in the range of 0.1 to 0.35. Reacts with the functional groups of the polymerreactionThe thermoplastic resin composition comprising a copolymer having a group is excellent in impact resistance and excellent in balance between physical properties such as heat resistance, solvent resistance, and workability and impact resistance. The headline and the present invention have been completed. It is not yet known that a compatibilizer having an intrinsic viscosity in a specific range exhibits a particularly excellent effect in improving the impact resistance of a thermoplastic resin composition containing a rubber-reinforced styrene resin and the polymer. .
[0011]
That is, the present invention is a rubber-reinforced styrene resin,Thermoplastic polyester, polyamide, polycarbonateIn the molecule with at least one polymer selected from the group consisting ofUsing the oxazoline group as a reactive groupA copolymer havingThe intrinsic viscosity of the copolymer is 0.1 to 0.35The present invention relates to a thermoplastic resin composition.
[0012]
Also,In the thermoplastic resin composition, the blending amount of the polymerizable monomer having the oxazoline group in the copolymer may be in the range of 0.1 wt% to 20 wt%.
[0013]
In the thermoplastic resin composition, the copolymer includes a polymerizable monomer having a reactive group that reacts with a functional group of the polymer, and a vinyl monomer copolymerizable with the polymerizable monomer. The chain transfer agent may be copolymerized using the above-described intrinsic viscosity so that the intrinsic viscosity is 0.1 to 0.35. The chain transfer agent may be an α-methylstyrene dimer.
[0014]
In addition, the present invention has the above copolymerreactionThe present invention relates to a thermoplastic resin composition in which the amount of groups is more than 0 and not more than 0.05 mol / kg with respect to the total amount of rubber-reinforced styrene resin, polymer and copolymer.
[0015]
The present invention relates to a thermoplastic resin group having a molecular weight distribution defined by weight average molecular weight / number average molecular weight of 3 or less in the copolymer.The molecular weight distribution may be 2 to 2.5.
[0016]
According to the above configuration, the thermoplastic resin composition according to the present invention includes a rubber-reinforced styrene resin and a polymer called a so-called engineering plastic (at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, and an amino group). As a compatibilizing agent for compatibilizing at least one polymer selected from the group consisting of thermoplastic polyesters, polyamides, and polycarbonates, and crystalline polymers), a copolymer having an intrinsic viscosity within the above range. By including the coalescence, the amount of the compatibilizer used for improving the impact resistance can be reduced (exceeding 0 to 0.05 mol / kg or less).
[0017]
Furthermore, according to the above configuration, it is possible to suppress a decrease in fluidity of each of the thermoplastic resin compositions, and sufficient impact resistance without degrading physical properties such as heat resistance, solvent resistance, and workability. Can be improved.
[0018]
In addition, by making the molecular weight distribution defined by weight average molecular weight / number average molecular weight 3 or less in the copolymer, it is possible to further suppress a decrease in fluidity of each thermoplastic resin composition, The impact resistance can be further sufficiently improved without deteriorating physical properties such as heat resistance, solvent resistance, and workability.
[0019]
Thereby, in the said structure, while being excellent in impact resistance, the thermoplastic resin composition with which physical properties, such as heat resistance, solvent resistance, and workability, and impact resistance were balanced can be obtained. That is, the thermoplastic resin composition according to the present invention is excellent in impact resistance and excellent in balance between physical properties such as heat resistance, solvent resistance, and workability and impact resistance.
[0020]
For this reason, the thermoplastic resin composition according to the present invention includes, for example, household electrical appliances such as refrigerators, washing machines, and vacuum cleaners, automobile interior and exterior parts, sundries, furniture building materials, etc., heat resistance, workability, and impact resistance. It can be used for a wide range of applications that require physical properties such as properties.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an embodiment of the present invention will be described in detail.
The thermoplastic resin composition according to the present invention (hereinafter referred to as the resin composition (I)) includes a rubber-reinforced styrene resin (hereinafter referred to as a rubber-reinforced styrene resin (A)), a carboxyl group, a hydroxyl group, an amino acid. A polymer having at least one functional group selected from the group consisting of a group (hereinafter referred to as polymer (X)), an intrinsic viscosity in the range of 0.1 to 0.35, and in the molecule, the carboxyl group, hydroxyl group, amino group Reacts with at least one functional group selected from the group consisting of groupsreactionAnd a copolymer having a group (hereinafter referred to as copolymer (Y)).
[0022]
The rubber-reinforced styrenic resin (A) is not particularly limited. ) Resin, HIPS (High Impact Polystyrene) resin, MBS (Methyl methylacrylate-Butadiene-Styrene) resin, etc., in the presence of a rubbery polymer, and if necessary, the aromatic vinyl single monomer Examples thereof include a polymer including a graft copolymer obtained by polymerizing another vinyl monomer copolymerizable with a monomer (hereinafter referred to as another vinyl monomer).
[0023]
The rubber-like polymer is not particularly limited, but specifically, for example, diene rubber such as polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer; ethylene-propylene copolymer Examples thereof include non-diene rubbers such as a polymer, ethylene-propylene non-conjugated diene copolymer, acrylic rubber, and chlorinated polyethylene. These rubbery polymers may be used alone or in a suitable mixture of two or more.
[0024]
The method for producing the rubbery polymer is not particularly limited, and can be produced by using various conventionally known methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization. The polymerization conditions for obtaining the rubbery polymer are not particularly limited.
[0025]
Although it does not specifically limit as said aromatic vinyl type monomer, Specifically, for example, styrene, (alpha) -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t -Methylstyrene, (alpha) -methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene etc. are mentioned. These aromatic vinyl monomers may be used alone or in a suitable mixture of two or more. Of these aromatic vinyl monomers, styrene and α-methylstyrene are particularly preferably used.
[0026]
The other vinyl monomer is not particularly limited, and specifically, for example, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; methyl acrylate, ethyl acrylate, butyl acrylate Unsaturated carboxylic acid alkyl esters such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate; maleimide-based monomers such as maleimide, N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide Examples include the body.
[0027]
These other vinyl monomers may be used alone or in a suitable mixture of two or more. Among the other vinyl monomers, acrylonitrile, methyl methacrylate, and N-phenylmaleimide are particularly preferably used.
[0028]
The graft copolymer production method, that is, a polymerization method for polymerizing an aromatic vinyl monomer and, if necessary, another vinyl monomer in the presence of a rubbery polymer, is particularly limited. However, various conventionally known methods such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like can be used.
[0029]
The blending ratio of each monomer (aromatic vinyl monomer and other vinyl monomers) and the rubber-like polymer in obtaining the graft copolymer is not particularly limited, The total amount of each monomer is preferably 80% to 20% by weight and the rubbery polymer is preferably 20% to 80% by weight.
[0030]
Furthermore, polymerization conditions other than the above blending ratio are not particularly limited, and may be set as appropriate so that the reaction is completed.
[0031]
Further, as the rubber-reinforced styrene resin (A), an aromatic vinyl polymer obtained by polymerizing the graft copolymer, an aromatic vinyl monomer, and, if necessary, another vinyl monomer. And a mixture thereof.
[0032]
As the aromatic vinyl monomer used as a raw material for the aromatic vinyl polymer and other vinyl monomers, the same monomers as those exemplified in the production of the graft copolymer may be used. Can be used. The method for producing the aromatic vinyl polymer is not particularly limited, and various conventionally known methods such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like can be used.
[0033]
The blending ratio of the aromatic vinyl monomer and the other vinyl monomer in obtaining the mixture of the aromatic vinyl polymer and the graft copolymer is not particularly limited. It is preferable to blend so as to be 10 wt% to 100 wt% of an aromatic vinyl monomer, and 90 wt% to 0 wt% of another vinyl monomer, and 30 wt% to 70 wt% of an aromatic vinyl monomer. More preferably, it is blended so that it becomes 70% by weight to 30% by weight of other vinyl monomers.
[0034]
The polymer (X) is a polymer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an amino group. Among the polymers (X), examples of the polymer having at least a carboxyl group include thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate; various acid-modified resins such as acid-modified polyethylene. Specific examples of the acid-modified resin include acid group-containing monomers (for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, 2-norbornene-5,6-dicarboxylic acid and the like). Saturated mono- and dicarboxylic acids) are copolymerized as copolymerizable components (for example, ethylene acrylic acid copolymer, acid-modified AS (acrylonitrile-styrene) resin, etc.), and the above acid group-containing monomers are graft copolymerized. Examples thereof include modified polyolefins modified by polymerization and acid-modified PPE (Polyphenylene ether) resin. Only one kind of these polymers may be used, or two or more kinds may be appropriately mixed and used.
[0035]
Specific examples of the polymer having at least a hydroxyl group include, for example, the above thermoplastic polyester; a polycarbonate such as an aromatic polycarbonate obtained by a reaction between a divalent phenol and a carbonate precursor such as phosgene or diphenyl carbonate; Although the copolymer obtained by copolymerizing a containing monomer as a copolymerization component is mentioned, it is not specifically limited. Only one kind of these polymers may be used, or two or more kinds may be appropriately mixed and used.
[0036]
Specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxymethylbenzyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxy. Examples thereof include methylbenzyl acrylate and 4-hydroxymethylbenzyl methacrylate, but are not particularly limited.
[0037]
Specific examples of the polymer having at least an amino group include, for example, polyamides such as nylon 6, nylon 66, 6/66 copolymer nylon, nylon 46, nylon 12, and the like; However, the copolymer is not particularly limited. Only one kind of these polymers may be used, or two or more kinds may be appropriately mixed and used.
[0038]
Specific examples of the amino group-containing monomer include, but are not particularly limited to, acrylamide and methacrylamide.
[0039]
The copolymer (Y) has an intrinsic viscosity in the range of 0.1 to 0.35 and reacts with at least one functional group selected from the group consisting of the carboxyl group, hydroxyl group, and amino group in the molecule.reactionThose having a group are preferred. More preferably, the molecular weight distribution defined by weight average molecular weight / number average molecular weight in the copolymer is 3 or less.
[0040]
The copolymer (Y) comprises polymerizable monomers having a reactive group that reacts with at least one functional group selected from the group consisting of the carboxyl group, the hydroxyl group, and the amino group, each other or with the polymerizable monomer. It can be easily obtained by copolymerizing with a polymerizable vinyl monomer.
[0041]
Reacts with the carboxyl groupreactionSpecific examples of the group include an oxazoline group, an epoxy group, and an amino group. Also reacts with hydroxyl groupsreactionExamples of the group include an acid anhydride group and an isocyanate group. Reacts with amino groupsreactionExamples of the group include an oxazoline group, an epoxy group, a carboxyl group, and an acid anhydride group.
[0042]
Among the polymerizable monomers, specific examples of the polymerizable monomer having an oxazoline group include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl- 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-5,5-dihydro-4H-1,3-oxazine, 4,4,6-trimethyl-2-vinyl-5,6-dihydro- Vinyl oxazolines such as 4H-1,3-oxazine, 2-isopropenyl-2-oxazoline, and 4,4-dimethyl-2-isopropenyl-2-oxazoline are exemplified, but are not particularly limited. Only one kind of these polymerizable monomers may be used, or two or more kinds may be appropriately mixed and used. Among the polymerizable monomers having the oxazoline group, 2-isopropenyl-2-oxazoline is preferably used.
[0043]
Specific examples of the polymerizable monomer having an epoxy group include glycidyl esters of unsaturated organic acids such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate; and allyl glycidyl ether. Although glycidyl ether etc. are mentioned, it does not specifically limit. Only one kind of these polymerizable monomers may be used, or two or more kinds may be appropriately mixed and used. Of the polymerizable monomers having an epoxy group, glycidyl acrylate and glycidyl methacrylate are preferably used.
[0044]
Specific examples of the polymerizable monomer having an acid anhydride group include maleic anhydride, phthalic anhydride, itaconic anhydride and the like, but are not particularly limited. Only one kind of these polymerizable monomers may be used, or two or more kinds may be appropriately mixed and used.
[0045]
Specific examples of the polymerizable monomer having an isocyanate group include, but are not limited to, vinyl isocyanate. Only one kind of these polymerizable monomers may be used, or two or more kinds may be appropriately mixed and used.
[0046]
Specific examples of the polymerizable monomer having an amino group include, but are not particularly limited to, acrylamide, methacrylamide, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and the like. Only one kind of these polymerizable monomers may be used, or two or more kinds may be appropriately mixed and used.
[0047]
Specific examples of the polymerizable monomer having a carboxyl group include, but are not particularly limited to, acrylic acid, methacrylic acid, maleic acid, phthalic acid, fumaric acid, and itaconic acid. Only one kind of these polymerizable monomers may be used, or two or more kinds may be appropriately mixed and used.
[0048]
Specific examples of the vinyl monomer copolymerizable with the polymerizable monomer include aromatic vinyl monomers such as styrene and α-methylstyrene; vinyl cyanide monomers such as acrylonitrile. (Meth) acrylate monomers such as methyl methacrylate and butyl acrylate. These vinyl monomers may be used alone or in a suitable mixture of two or more.
[0049]
Reacts with at least one functional group selected from the group consisting of the carboxyl group, hydroxyl group and amino group in the copolymer (Y).reactionThe total amount of polymerizable monomers having a group is not particularly limited, but is preferably in the range of 0.1% by weight to 20% by weight, and more preferably in the range of 0.5% by weight to 15% by weight.
[0050]
If the total blending amount of the polymerizable monomers is less than 0.1% by weight, the resin composition (I) finally obtained may not be able to fully exhibit the impact resistance, which is preferable. Absent. On the other hand, if the total amount of the polymerizable monomers exceeds 20% by weight, the processability may be lowered, which is not preferable.
[0051]
The method for producing the copolymer (Y) is not particularly limited, and various conventionally known methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and the like can be used.
[0052]
In the method for producing the copolymer (Y), examples of the solvent that can be used when the monomer is copolymerized by employing the solution polymerization method include aromatic hydrocarbons such as toluene and xylene; Acetic esters such as ethyl and butyl acetate; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aliphatic alcohols such as isopropanol, n-butanol and iso-butanol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl Although alkylene glycol monoalkyl ethers, such as ether, are mentioned, it is not specifically limited. Only one kind of these solvents may be used, or two or more kinds may be appropriately mixed and used. Moreover, the usage-amount of these solvents is not specifically limited.
[0053]
Moreover, when each monomer is copolymerized, a polymerization initiator can be used. Specific examples of the polymerization initiator include ordinary radical polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, and di-t-butyl peroxide, but are particularly limited. It is not a thing. Moreover, the usage-amount of a polymerization initiator is not specifically limited.
[0054]
In addition, the reaction temperature and reaction time when copolymerizing each monomer are not particularly limited, and depending on the type of monomer used and polymerization initiator, etc., so that the polymerization reaction is completed, What is necessary is just to set suitably.
[0055]
Further, a chain transfer agent such as α-methylstyrene dimer or a polymerization regulator may be used in the reaction system for the purpose of adjusting the intrinsic viscosity. For the purpose of adjusting the intrinsic viscosity, the obtained copolymer may be heat-treated after the polymerization reaction.
[0056]
Here, the intrinsic viscosity [η] is a general formula
[0057]
[Expression 1]

[0058]
It is a viscosity represented by. Where η_spIs the specific viscosity, η_rIndicates relative viscosity, {η_sp= (Η−η₀) / Η₀= Η_r-1}. C represents the volume concentration (weight / volume) of the solution. That is, the intrinsic viscosity is determined by measuring the viscosities of solutions having different concentrations, and (η_sp/ C) or (lnη_rIn the relationship between / c) and volume concentration, a value obtained by extrapolating c to 0 by an appropriate method is shown.
[0059]
In the case of obtaining the intrinsic viscosity, specifically, the copolymer (Y) is dissolved in dimethylformamide to obtain solutions having different concentrations, for example, concentrations of 1 g / 100 ml, 0.5 g / 100 ml, 0.3 Three kinds of solutions of g / 100 ml are prepared, and after preparing this solution at 30 ° C., the viscosity is measured with an Ubbelohde viscometer, and the concentration can be extrapolated to zero.
[0060]
It is preferable to design the intrinsic viscosity of the copolymer (Y) to be in the range of 0.1 to 0.35. When the intrinsic viscosity of the copolymer (Y) is within the above range, a decrease in fluidity of the resulting resin composition (I) can be suppressed, and heat resistance, solvent resistance, workability, etc. It is possible to sufficiently improve the impact resistance without deteriorating the physical properties. Thereby, while being excellent in impact resistance, the resin composition (I) with which physical properties, such as heat resistance, solvent resistance, and workability, and impact resistance were balanced can be obtained.
[0061]
On the other hand, if the intrinsic viscosity of the copolymer (Y) is less than 0.1 or greater than 0.35, it is difficult to sufficiently improve the impact resistance of the resin composition (I). In addition, the amount of copolymer (Y) added required to improve impact resistance increases. Furthermore, the fluidity of the resin composition (I) is lowered, and the balance between physical properties such as heat resistance, solvent resistance, and workability and impact resistance is deteriorated, which is not preferable.
[0062]
The copolymer (Y) is preferably designed so that the molecular weight distribution defined by weight average molecular weight / number average molecular weight is 3 or less. When the molecular weight distribution of the copolymer (Y) is within the above range, a decrease in fluidity of the resulting resin composition (I) can be suppressed, and heat resistance, solvent resistance, workability, etc. It is possible to sufficiently improve the impact resistance without deteriorating the physical properties. Thereby, while being excellent in impact resistance, the resin composition (I) with which physical properties, such as heat resistance, solvent resistance, and workability, and impact resistance were balanced can be obtained.
[0063]
On the other hand, when the molecular weight distribution of the copolymer (Y) exceeds 3, it is difficult to sufficiently improve the impact resistance of the resin composition (I), and in order to improve the impact resistance. The amount of copolymer (Y) required increases. Furthermore, the fluidity of the resin composition (I) is lowered, and the balance between physical properties such as heat resistance, solvent resistance, and workability and impact resistance is deteriorated, which is not preferable.
[0064]
The resin composition (I) according to the present invention can be easily obtained by mixing the rubber-reinforced styrene resin (A), the polymer (X), and the copolymer (Y).
[0065]
The blending ratio of the rubber-reinforced styrene resin (A) and the polymer (X) is not particularly limited, but the rubber-reinforced styrene resin is used with respect to 90 parts by weight to 10 parts by weight of the polymer (X). It is preferable to blend (A) at a ratio of 10 to 90 parts by weight.
[0066]
If the blending ratio of the rubber-reinforced styrene resin (A) is less than 10 parts by weight, the resulting resin composition (I) is preferable because it cannot sufficiently exhibit physical properties such as impact resistance and workability. Absent. On the other hand, if the blending ratio of the rubber-reinforced styrene resin (A) is more than 90 parts by weight, the resin composition (I) is preferable because it cannot sufficiently exhibit physical properties such as heat resistance and solvent resistance. Absent.
[0067]
Moreover, the said copolymer (Y) with respect to the total amount of the said rubber reinforced styrene resin (A), polymer (X), and a copolymer (Y) has.reactionThe amount of the group is preferably more than 0 and 0.05 mol / kg or less.
[0068]
The copolymer (Y) has a total amount of the rubber-reinforced styrene resin (A), the polymer (X), and the copolymer (Y).reactionIf the amount of the group exceeds 0.05 mol / kg, physical properties such as heat resistance, solvent resistance, and processability of the obtained resin composition (I) may be deteriorated, which is not preferable.
[0069]
The mixing method of the rubber-reinforced styrene resin (A), the polymer (X), and the copolymer (Y) is not particularly limited, and the rubber-reinforced styrene resin (A), the polymer (X), And the copolymer (Y) may be mixed at the same time, and after the two components of the rubber-reinforced styrene resin (A), the polymer (X), and the copolymer (Y) are mixed in advance, the remaining 1 The components may be mixed. Further, the order of mixing the rubber-reinforced styrene resin (A), the polymer (X), and the copolymer (Y) is not particularly limited.
[0070]
Furthermore, the state of each said component at the time of mixing is not specifically limited, It can mix in various states, such as a pellet, bead, and powder. For mixing the above components, specifically, conventionally known kneaders such as a high-speed stirrer such as a Banbury mixer, a roll, a single-screw or multi-screw extruder, etc. can be used, but are particularly limited. It is not a thing.
[0071]
The combination of the polymer (X) and the copolymer (Y) is not particularly limited, but the polymer (X) is a polymer having a carboxyl group, and the copolymer (Y) is an oxazoline group and A combination that is a copolymer having an epoxy group is particularly preferable in view of the physical properties of the resulting resin composition (I).
[0072]
The thermoplastic resin composition according to the present invention (hereinafter referred to as resin composition (II)) is at least one selected from the group consisting of rubber-reinforced styrene resin (A), thermoplastic polyester, polyamide, and polycarbonate. And a copolymer having an intrinsic viscosity in the range of 0.1 to 0.35 and having an oxazoline group and / or an epoxy group in the molecule (hereinafter referred to as a copolymer). Polymer (denoted as Z)).
[0073]
The rubber-reinforced styrene resin (A) is not particularly limited, and the same compounds as the exemplified compounds can be used. One type of the rubber-reinforced styrene resin (A) may be used, or two or more types may be appropriately mixed and used.
[0074]
The polymer (W) is at least one polymer selected from the group consisting of thermoplastic polyester, polyamide, and polycarbonate. The thermoplastic polyester, polyamide, and polycarbonate are not particularly limited, and similar compounds corresponding to the compounds exemplified in the polymer (X) can be used. Only one kind of these polymers (W) may be used, or two or more kinds may be appropriately mixed and used.
[0075]
The copolymer (Z) is a copolymer having an intrinsic viscosity in the range of 0.1 to 0.35 and having an oxazoline group and / or an epoxy group in the molecule.
[0076]
The copolymer (Z) can be easily obtained by copolymerizing the polymerizable monomers having the oxazoline group or the epoxy group with each other or a vinyl monomer copolymerizable with the polymerizable monomer. Can do.
[0077]
The polymerizable monomer having an oxazoline group and the polymerizable monomer having an epoxy group are not particularly limited, and similar compounds corresponding to the compounds exemplified in the copolymer (Y) can be used. . Each said polymerizable monomer may use only 1 type, and may mix and use 2 or more types suitably.
[0078]
The vinyl monomer copolymerizable with each polymerizable monomer is not particularly limited, and the same compounds as those exemplified in the method for producing the copolymer (Y) may be used. it can. Only one kind of the vinyl monomer may be used, or two or more kinds may be appropriately mixed and used.
[0079]
In addition, it does not specifically limit as a manufacturing method of the said copolymer (Z), The manufacturing method and manufacturing conditions similar to the manufacturing method illustrated in the said copolymer (Y) can be used.
[0080]
The intrinsic viscosity of the copolymer (Z) is preferably designed to be in the range of 0.1 to 0.35. When the intrinsic viscosity of the copolymer (Z) is within the above range, a decrease in fluidity of the resulting resin composition (II) can be suppressed, and heat resistance, solvent resistance, workability, etc. It is possible to sufficiently improve the impact resistance without deteriorating the physical properties. As a result, it is possible to obtain a resin composition (II) that is excellent in impact resistance and has a balance between physical properties such as heat resistance, solvent resistance, and workability, and impact resistance.
[0081]
On the other hand, if the intrinsic viscosity of the copolymer (Z) is less than 0.1 or greater than 0.35, it is difficult to sufficiently improve the impact resistance of the resin composition (II). Also, the amount of copolymer (Z) added to improve impact resistance increases. Furthermore, the flowability of the resin composition (II) is lowered, and the balance between physical properties such as heat resistance, solvent resistance, and workability and impact resistance is unfavorable.
[0082]
The resin composition (II) according to the present invention can be easily obtained by mixing the rubber-reinforced styrene resin (A), the polymer (W), and the copolymer (Z).
[0083]
The blending ratio of the rubber-reinforced styrene resin (A) and the polymer (W) is not particularly limited, but the rubber-reinforced styrene resin is used with respect to 90 parts by weight to 10 parts by weight of the polymer (W). It is preferable to blend (A) at a ratio of 10 to 90 parts by weight.
[0084]
If the blending ratio of the rubber-reinforced styrene resin (A) is less than 10 parts by weight, the resulting resin composition (II) is preferable because it cannot sufficiently exhibit physical properties such as impact resistance and workability. Absent. On the other hand, if the blending ratio of the rubber-reinforced styrene resin (A) is more than 90 parts by weight, the resin composition (II) is not preferable because it cannot sufficiently exhibit physical properties such as heat resistance and solvent resistance. Absent.
[0085]
Moreover, the said copolymer (Z) with respect to the total amount of the said rubber reinforced styrene resin (A), a polymer (W), and a copolymer (Z) has.reactionThe amount of the group is preferably more than 0 and 0.05 mol / kg or less.
[0086]
The copolymer (Z) has a total amount of the rubber-reinforced styrene resin (A), the polymer (W), and the copolymer (Z).reactionIf the amount of the group exceeds 0.05 mol / kg, physical properties such as heat resistance, solvent resistance and processability of the obtained resin composition (II) may be lowered, which is not preferable.
[0087]
The mixing method of the rubber-reinforced styrene-based resin (A), the polymer (W), and the copolymer (Z) and the state of each component during mixing are particularly limited as in the case of the resin composition (I). Is not to be done.
[0088]
The thermoplastic resin composition (hereinafter referred to as resin composition (III)) according to the present invention comprises a rubber-reinforced styrene resin (A), a crystalline polymer (hereinafter referred to as polymer (B)), an intrinsic viscosity. Is in the range of 0.1 to 0.35, and in the molecule, at least one selected from the group consisting of an oxazoline group, an epoxy group, an acid anhydride group, and an isocyanate groupreactionA copolymer containing a group (hereinafter referred to as copolymer (C)).
[0089]
The rubber-reinforced styrene resin (A) is not particularly limited, and the same compounds as the exemplified compounds can be used. One type of the rubber-reinforced styrene resin (A) may be used, or two or more types may be appropriately mixed and used.
[0090]
Specific examples of the polymer (B) include thermoplastic polyesters, polyamides, polyacetals, and polyolefins, but are not particularly limited as long as they are crystalline thermoplastic resins. These crystalline polymers (B) may be used alone or in a suitable mixture of two or more.
[0091]
The thermoplastic polyester is not particularly limited, and the same compounds as those exemplified in the polymer (X) can be used. One type of the thermoplastic polyester may be used, or two or more types may be appropriately mixed and used.
[0092]
The polyamide is not particularly limited, and the same compounds as those exemplified in the polymer (X) can be used. Only one kind of the polyamide may be used, or two or more kinds may be appropriately mixed and used.
[0093]
The polyacetal is obtained by polymerizing formaldehyde and increasing the molecular weight. Specifically, for example, Duracon (trade name: manufactured by Polyplastics Co., Ltd.), Tenac (produced by Asahi Kasei Kogyo Co., Ltd.), Yupinal (Mitsubishi Gas Co., Ltd.). Are not particularly limited. These polyacetals may be used alone or in a suitable mixture of two or more.
[0094]
Specific examples of the polyolefin include, but are not particularly limited to, polyethylene and polypropylene. These polyolefins may be used alone or in a suitable mixture of two or more.
[0095]
The copolymer (C) has an intrinsic viscosity in the range of 0.1 to 0.35, and has at least one selected from the group consisting of an oxazoline group, an epoxy group, an acid anhydride group, and an isocyanate group in the molecule.reactionIt is a copolymer having a group.
[0096]
The copolymer (C) is selected from the group consisting of an oxazoline group, an epoxy group, an acid anhydride group, and an isocyanate group.reactionThe polymerizable monomer having a group can be easily obtained by copolymerizing with each other or with another vinyl monomer copolymerizable with the polymerizable monomer.
[0097]
Examples of the polymerizable monomer having an oxazoline group, the polymerizable monomer having an epoxy group, the polymerizable monomer having an acid anhydride group, and the polymerizable monomer having an isocyanate group include the compounds exemplified in the copolymer (Y). Corresponding similar compounds can be used. Only one kind of these polymerizable monomers may be used, or two or more kinds may be appropriately mixed and used.
[0098]
The vinyl monomer copolymerizable with each polymerizable monomer is not particularly limited, and the same compounds as those exemplified in the method for producing the copolymer (Y) may be used. it can. Only one kind of the vinyl monomer may be used, or two or more kinds may be appropriately mixed and used.
[0099]
Moreover, it does not specifically limit as a manufacturing method of the said copolymer (C), The manufacturing method and manufacturing conditions similar to the manufacturing method illustrated in the said copolymer (Y) can be used.
[0100]
The intrinsic viscosity of the copolymer (C) is preferably designed to be in the range of 0.1 to 0.35. When the intrinsic viscosity of the copolymer (C) is within the above range, a decrease in fluidity of the resulting resin composition (III) can be suppressed, and heat resistance, solvent resistance, workability, etc. It is possible to sufficiently improve the impact resistance without deteriorating the physical properties. Thereby, while being excellent in impact resistance, the resin composition (III) in which physical properties, such as heat resistance, solvent resistance, and workability, and the impact resistance are balanced can be obtained.
[0101]
On the other hand, if the intrinsic viscosity of the copolymer (C) is less than 0.1 or greater than 0.35, it is difficult to sufficiently improve the impact resistance of the resin composition (III). In addition, the amount of copolymer (C) added to improve impact resistance increases. Furthermore, the flowability of the resin composition (III) is lowered, and the balance between physical properties such as heat resistance, solvent resistance, and workability and impact resistance is unfavorable.
[0102]
The resin composition (III) according to the present invention can be easily obtained by mixing the rubber-reinforced styrene resin (A), the polymer (B), and the copolymer (C).
[0103]
The blending ratio of the rubber-reinforced styrenic resin (A) and the polymer (B) is not particularly limited, but the rubber-reinforced styrenic resin with respect to 90 to 10 parts by weight of the polymer (B). It is preferable to blend (A) at a ratio of 10 to 90 parts by weight.
[0104]
If the blending ratio of the rubber-reinforced styrene resin (A) is less than 10 parts by weight, the resulting resin composition (III) is preferable because it cannot sufficiently exhibit physical properties such as impact resistance and workability. Absent. On the other hand, if the blending ratio of the rubber-reinforced styrene resin (A) is more than 90 parts by weight, the resulting resin composition (III) cannot sufficiently exhibit physical properties such as heat resistance and chemical resistance. It is not preferable.
[0105]
Moreover, the said copolymer (C) with respect to the total amount of the said rubber reinforced styrene-type resin (A), a polymer (B), and a copolymer (C) has.reactionThe amount of the group is preferably more than 0 and 0.05 mol / kg or less.
[0106]
The copolymer (C) has a total amount of the rubber-reinforced styrene resin (A), the polymer (B), and the copolymer (C).reactionIf the amount of the group exceeds 0.05 mol / kg, physical properties such as heat resistance, solvent resistance and processability of the obtained resin composition (III) may be lowered, which is not preferable.
[0107]
The mixing method of the rubber-reinforced styrene-based resin (A), the polymer (B), and the copolymer (C) and the state of each component during mixing are particularly limited as in the case of the resin composition (I). Is not to be done.
[0108]
In addition, the above resin compositions (I), (II), and (III) include reinforcing materials and fillers such as pigments and dyes, glass fibers, metal fibers, carbon fibers, and metal flakes, as required. Various conventionally known additives such as an inhibitor, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antistatic agent, a lubricant, a plasticizer, and a flame retardant may be added. Only one type of these additives may be used, or two or more types may be appropriately mixed and used. Moreover, the addition amount of these additives is not specifically limited.
[0109]
Further, according to the desired physical properties, other thermoplastic resins such as polyacetal, polymethyl methacrylate, vinyl chloride and the like may be appropriately blended with the resin compositions (I), (II), and (III). . Further, each of the resin compositions (I), (II), and (III) may be used singly or may be appropriately mixed and used.
[0110]
As described above, the thermoplastic resin composition according to the present invention has an intrinsic viscosity of 0.1 to 0.35 as a compatibilizing agent for compatibilizing the rubber-reinforced styrene resin (A) and each polymer. Yes, it reacts with the functional group of each polymer in the moleculereactionBy including a copolymer having a group, the amount of the compatibilizer used for improving impact resistance can be suppressed to a small amount (over 0 to 0.05 mol / kg or less).
[0111]
Furthermore, according to the present invention, it is possible to suppress a decrease in fluidity of each resin composition (I), (II), and (III) to be obtained, and to improve physical properties such as heat resistance, solvent resistance, and workability. The impact resistance can be sufficiently improved without lowering. Thereby, while being excellent in impact resistance, the resin composition which balanced physical properties, such as heat resistance, solvent resistance, and workability, and impact resistance can be obtained.
[0112]
That is, each resin composition (I), (II), and (III) according to the present invention is excellent in impact resistance and balance between physical properties such as heat resistance, solvent resistance, and workability and impact resistance. Is excellent. The processability can be evaluated by the fluidity of each resin composition (I), (II), and (III).
[0113]
Therefore, each of the resin compositions (I), (II), and (III) is, for example, a home electric appliance such as a refrigerator, a washing machine, and a vacuum cleaner, an interior / exterior part of an automobile, a miscellaneous product, and a furniture building material. It can be used in a wide range of applications that require physical properties such as heat resistance, solvent resistance, workability, and impact resistance.
[0114]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these. Moreover, the impact resistance, heat resistance, processability, and molecular weight distribution of the thermoplastic resin composition were evaluated by the following methods.
[0115]
The impact resistance was evaluated by measuring a so-called ¼ ″ notched Izod impact strength of a test piece obtained by molding the obtained resin composition. That is, a test piece with a V-shaped notch (cut) in the center was supported at one end, hit with a hammer from the same side as the notch, and the amount of energy absorbed by the breakage was determined. In addition, the measurement of the said impact resistance was implemented based on JIS K 7110 using the No. 2 test piece as described in JIS K 7110.
[0116]
The heat resistance was evaluated by measuring the heat distortion temperature (deflection temperature under load) of a test piece obtained by molding the obtained resin composition. That is, 18.5 kgf / cm at the center of the test piece (12.5 mm × 6 mm)²The load corresponding to the stress of 1 was added, the temperature was raised at a rate of 2 ° C./min, and the temperature at which the test piece was bent by 0.26 mm was defined as the load deflection temperature. In addition, the said heat resistance measurement was implemented based on JISK7207.
[0117]
The processability was evaluated by measuring the fluidity of the obtained resin composition. That is, the obtained resin composition was extruded from a predetermined test apparatus under the conditions of a temperature of 240 ° C. and a load of 10 kg, and the extrusion amount (MFR) per 10 minutes was determined. That is, the larger the MFR value, the higher the fluidity. In addition, the measurement of the said fluidity | liquidity was implemented based on JISK7210.
[0118]
The intrinsic viscosity of the copolymer was determined by the following method. First, the obtained copolymer was dissolved in dimethylformamide to prepare three types of solutions having concentrations of 1 g / 100 ml, 0.5 g / 100 ml, and 0.3 g / 100 ml. Then, after preparing these three kinds of solutions at 30 ° C., the viscosity was measured with an Ubbelohde viscometer and the concentration was extrapolated to 0.
[0119]
In the molecular weight distribution, the weight average molecular weight was measured based on the GPC (Gel Permeation Chromatography) method, while the number average molecular weight was also measured based on the GPC method and calculated from the results.
[0120]
[Example 1]
First, a reaction vessel equipped with a reflux tube, a temperature sensor, a gas introduction tube, a dropping device, and a stirring device was sufficiently replaced with nitrogen gas. Next, 100 parts of toluene as a solvent and 1 part of α-methylstyrene dimer as a chain transfer agent were charged into the reaction vessel. On the other hand, in the dropping device, 70 parts of styrene, which is an aromatic vinyl monomer, 25 parts of acrylonitrile, which is another vinyl monomer, and 2-isopropenyl-2-2, which is a polymerizable monomer having an oxazoline group. A mixture with 5 parts of oxazoline and 2 parts of t-butylperoxy-2-ethylhexanoate as a polymerization initiator were charged.
[0121]
Next, after raising the temperature of the reaction solution to 100 ° C., the mixture and the polymerization initiator in the dropping device were gradually added dropwise to the reaction solution over 4 hours with stirring.
[0122]
After completion of the dropwise addition, the reaction was completed by further stirring the above reaction solution for 3 hours. As a result, a pale yellow viscous polymer solution was obtained. Subsequently, this polymer solution was devolatilized under reduced pressure by a predetermined method and pelletized to obtain an oxazoline group-modified copolymer (hereinafter referred to as copolymer (a)). The intrinsic viscosity of the copolymer (a) at 30 ° C. measured using dimethylformamide as a solvent was 0.27, and the molecular weight distribution of the copolymer (a) was 2.3.
[0123]
Subsequently, 50 parts of a commercially available ABS resin (manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: ABS # 10; hereinafter referred to as ABS) as a rubber-reinforced styrene resin (A), a commercially available polybutylene terephthalate as an engineering plastic ( 50 parts of a saturated polyester resin manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Novador 5010; hereinafter referred to as PBT), and 3 parts of the above copolymer (a) are mixed and melt mixed in a twin screw extruder. A pellet-shaped resin composition (hereinafter referred to as resin composition (1)) was obtained.
[0124]
3 parts of the copolymer (a) corresponds to 0.0135 mol / kg in terms of the content of oxazoline groups. Moreover, about the said resin composition (1), fluidity | liquidity was measured by the method mentioned above.
[0125]
Then, the test piece was created from the said resin composition (1) using the injection molding machine. The impact resistance and heat resistance of this test piece were measured by the method described above. Table 1 shows the mixing conditions of the ABS, PBT, and copolymer (a) and the test results.
[0126]
[Table 1]

[0127]
[Example 2]
In Example 1, except that the addition amount of the copolymer (a) was changed from 3 parts to 5 parts, a pellet-shaped resin composition (hereinafter, resin composition ( 2)) was obtained. 5 parts of the copolymer (a) corresponds to 0.0225 mol / kg in terms of the content of the oxazoline group. Further, the fluidity of the resin composition (2) was measured by the same method as in Example 1.
[0128]
Then, the test piece was created from the said resin composition (2) using the injection molding machine. The impact resistance and heat resistance of this test piece were measured in the same manner as in Example 1. Table 1 shows the mixing conditions of the ABS, PBT, and copolymer (a) and the test results.
[0129]
Example 3
In Example 1, except that the amount of α-methylstyrene dimer was changed from 1 part to 3 parts, the same reaction and operation as in Example 1 were performed to obtain an oxazoline group-modified copolymer (hereinafter referred to as copolymer ( b)) was obtained. The intrinsic viscosity of the copolymer (b) measured at 30 ° C. measured using dimethylformamide as a solvent was 0.16, and the molecular weight distribution of the copolymer (b) was 2.1.
[0130]
Next, in Example 1, a pellet-shaped resin composition (hereinafter referred to as “Pellet-shaped resin composition”) was used in the same manner as in Example 1, except that 3 parts of copolymer (b) was used instead of copolymer (a). Resin composition (3)) was obtained. 3 parts of the copolymer (b) correspond to 0.0135 mol / kg in terms of oxazoline group content. Further, the fluidity of the resin composition (3) was measured by the same method as in Example 1.
[0131]
Thereafter, a test piece was prepared from the resin composition (3) using an injection molding machine. The impact resistance and heat resistance of this test piece were measured in the same manner as in Example 1. Table 1 summarizes the mixing conditions of the ABS, PBT, and copolymer (b) and the test results.
[0132]
Example 4
In Example 3, except that the addition amount of the copolymer (b) was changed from 3 parts to 5 parts, a pellet-shaped resin composition (hereinafter, resin composition ( 4)) was obtained. 5 parts of the copolymer (b) correspond to 0.0225 mol / kg in terms of oxazoline group content. Further, the fluidity of the resin composition (4) was measured by the same method as in Example 1.
[0133]
Then, the test piece was created from the said resin composition (4) using the injection molding machine. The impact resistance and heat resistance of this test piece were measured by the same method as in Example 3, that is, Example 1. Table 1 summarizes the mixing conditions of the ABS, PBT, and copolymer (b) and the test results.
[0134]
[Comparative Example 1]
50 parts of ABS and 50 parts of PBT were mixed and melt-mixed with a twin-screw extruder to be pelletized to obtain a pellet-shaped comparative resin composition (hereinafter referred to as resin composition (5)). Further, the fluidity of the resin composition (5) was measured by the same method as in Example 1.
[0135]
Then, the test piece was created from the said resin composition (5) using the injection molding machine. The impact resistance and heat resistance of this test piece were measured in the same manner as in Example 1. The mixing conditions of the ABS and PBT and the test results are shown together in Table 2.
[0136]
[Table 2]

[0137]
[Comparative Example 2]
In Example 1, except that the α-methylstyrene dimer was not added, the same reaction and operation as in Example 1 were performed to obtain a comparative oxazoline group-modified copolymer (hereinafter referred to as copolymer (c)). I wrote). The intrinsic viscosity of the copolymer (c) at 30 ° C. measured using dimethylformamide as a solvent was 0.44, and the molecular weight distribution of the copolymer (c) was 2.3.
[0138]
Next, in Example 1, a pellet-shaped comparative resin composition was used in the same manner as in Example 1 except that 3 parts of copolymer (c) was used instead of copolymer (a). (Hereinafter referred to as the resin composition (6)). 3 parts of the copolymer (c) correspond to 0.0135 mol / kg in terms of oxazoline group content. Further, the fluidity of the resin composition (6) was measured by the same method as in Example 1.
[0139]
Then, the test piece was created from the said resin composition (6) using the injection molding machine. The impact resistance and heat resistance of this test piece were measured in the same manner as in Example 1. Table 2 summarizes the mixing conditions of the ABS, PBT, and copolymer (c) and the test results.
[0140]
[Comparative Example 3]
In Comparative Example 2, a pellet-shaped resin composition (hereinafter, resin composition ( 7)) was obtained. 5 parts of the copolymer (c) corresponds to 0.0225 mol / kg in terms of the content of the oxazoline group. Further, the fluidity of the resin composition (7) was measured by the same method as in Example 1.
[0141]
Thereafter, a test piece was prepared from the resin composition (7) using an injection molding machine. The impact resistance and heat resistance of this test piece were measured by the same method as in Comparative Example 2, that is, Example 1. Table 2 summarizes the mixing conditions of the ABS, PBT, and copolymer (c) and the test results.
[0142]
[Comparative Example 4]
In Example 1, except that the amount of α-methylstyrene dimer was changed from 1 part to 5 parts, the same reaction and operation as in Example 1 were carried out to produce a comparative oxazoline-modified copolymer (hereinafter referred to as copolymer). Combined (denoted as d)) was obtained. The intrinsic viscosity of the copolymer (d) at 30 ° C. measured using dimethylformamide as a solvent was 0.07, and the molecular weight distribution of the copolymer (d) was 2.0.
[0143]
Next, in Example 1, a pellet-shaped comparative resin composition was used in the same manner as in Example 1 except that 5 parts of copolymer (d) was used instead of copolymer (a). (Hereinafter referred to as the resin composition (8)). The above copolymer (d) 5 parts corresponds to 0.0225 mol / kg in terms of oxazoline group content. Further, the fluidity of the resin composition (8) was measured by the same method as in Example 1.
[0144]
Then, the test piece was created from the said resin composition (8) using the injection molding machine. The impact resistance and heat resistance of this test piece were measured in the same manner as in Example 1. Table 2 summarizes the mixing conditions of the ABS, PBT, and copolymer (d) and the test results.
[0145]
Example 5
50 parts of ABS as a rubber-reinforced styrene resin (A), 50 parts of a commercially available polycarbonate (manufactured by Teijin Chemicals Ltd., trade name: Panlite L-1250; hereinafter referred to as PC) as an engineering plastic, and the above copolymer (A) 5 parts were mixed and melt-mixed with a twin-screw extruder to obtain a pellet-shaped resin composition (hereinafter referred to as a resin composition (9)). Further, the fluidity of the resin composition (9) was measured by the same method as in Example 1.
[0146]
Then, the test piece was created from the said resin composition (9) using the injection molding machine. The impact resistance and heat resistance of this test piece were measured by a predetermined method. Table 1 shows the mixing conditions of the ABS, PC, and copolymer (a) and the test results.
[0147]
[Comparative Example 5]
In Example 5, instead of the copolymer (a), a pellet-shaped comparative resin composition (hereinafter, referred to as “Example 5”) was used except that 5 parts of the copolymer (c) was used. Resin composition (10)) was obtained. Further, the fluidity of the resin composition (10) was measured by the same method as in Example 1.
[0148]
Then, the test piece was created from the said resin composition (10) using the injection molding machine. The impact resistance and heat resistance of this test piece were measured in the same manner as in Example 1. Table 2 summarizes the mixing conditions of the ABS, PC, and copolymer (c) and the test results.
[0149]
[Comparative Example 6]
50 parts of ABS and 50 parts of PC were mixed and melt-mixed with a twin-screw extruder and pelletized to obtain a pellet-shaped comparative resin composition (hereinafter referred to as resin composition (11)). Further, the fluidity of the resin composition (11) was measured by the same method as in Example 1.
[0150]
Then, the test piece was created from the said resin composition (11) using the injection molding machine. The impact resistance and heat resistance of this test piece were measured in the same manner as in Example 1. The mixing conditions of the ABS and PC and the test results are shown together in Table 2.
[0151]
As is clear from the results described in Table 1 and Table 2, the resin compositions (1) to (4) obtained in this example are resins obtained in Comparative Examples without reducing heat resistance. The impact resistance is improved as compared with the compositions (5) to (8). In addition, the resin composition (9) obtained in this example has improved impact resistance compared to the resin compositions (10) and (11) obtained in the comparative examples without reducing the heat resistance. It has become a thing.
[0152]
Furthermore, for each test piece obtained in this example, when the solvent resistance was visually observed, the deterioration of the test piece surface due to the solvent was clearly improved as compared with the deterioration of the test piece surface of the comparative example. It was.
[0153]
Example 6
First, a reaction vessel equipped with a reflux tube, a temperature sensor, a gas introduction tube, a dropping device, and a stirring device was sufficiently replaced with nitrogen gas. Next, 100 parts of toluene as a solvent and 1 part of α-methylstyrene dimer as a chain transfer agent were charged into the reaction vessel.
[0154]
On the other hand, a dropping apparatus was charged with a mixture of 24.7 parts of acrylonitrile, 69 parts of styrene, 6.3 parts of glycidyl methacrylate, and 2 parts of t-butylperoxy-2-ethylhexanoate as a polymerization initiator.
[0155]
Next, after the temperature of the solution in the reaction vessel was raised to 100 ° C., the mixture and the polymerization initiator in the dropping apparatus were gradually added dropwise to the reaction solution over 4 hours with vigorous stirring.
[0156]
After completion of the dropwise addition, the reaction solution was aged by further stirring for 3 hours to complete the reaction. As a result, a pale yellow viscous polymer solution was obtained. Next, this polymer solution was devolatilized under reduced pressure by a predetermined method and pelletized to obtain an epoxy group-modified copolymer (hereinafter referred to as copolymer (e)). The intrinsic viscosity of the copolymer (e) at 30 ° C. measured using dimethylformamide as a solvent was 0.27, and the molecular weight distribution of the copolymer (e) was 2.2.
[0157]
Next, 50 parts of the ABS, 50 parts of the PBT, and 5 parts of the copolymer (e) are mixed and melt-mixed with a twin-screw extruder to form a pellet-shaped resin composition (hereinafter referred to as resin composition). (Denoted as (12)). 5 parts of the copolymer (e) correspond to 0.0225 mol / kg in terms of epoxy group content. Further, the fluidity of the resin composition (12) was measured by the method described above.
[0158]
Then, the test piece was created from the said resin composition (12) using the injection molding machine. The impact resistance and heat resistance of this test piece were measured by the method described above. Table 1 shows the mixing conditions of the ABS, PBT, and copolymer (e) and the test results.
[0159]
As is apparent from the results in Table 1, in the thermoplastic resin composition of the present invention, even when the epoxy group-modified copolymer (e) is used, the heat resistance is maintained as in the case of the oxazoline group-modified copolymer. However, impact resistance can be improved.
[0160]
As is clear from the results of Tables 1 and 2, each resin composition of Examples 1 to 6 has a molecular weight distribution of 2 to 2.3 without reducing heat resistance. It can be seen that the obtained Izod has high impact resistance.
[0161]
From this, in the thermoplastic resin composition of the present invention,reactionBy making the molecular weight distribution in the copolymer having a group 3 or less, more preferably 2 to 2.5, it is possible to further improve the impact resistance while maintaining the heat resistance in the obtained thermoplastic resin composition. It becomes.
[0162]
【The invention's effect】
As described above, the thermoplastic resin composition of the present invention comprises a rubber-reinforced styrene resin,Thermoplastic polyester, polyamide, polycarbonateIn the molecule with at least one polymer selected from the group consisting ofUsing the oxazoline group as a reactive groupA copolymer havingThe intrinsic viscosity of the copolymer is 0.1 to 0.35This is a configuration.
[0163]
Also,In the thermoplastic resin composition, the blending amount of the polymerizable monomer having the oxazoline group in the copolymer may be in the range of 0.1 wt% to 20 wt%.
[0164]
In the thermoplastic resin composition, the copolymer includes a polymerizable monomer having a reactive group that reacts with a functional group of the polymer, and a vinyl monomer copolymerizable with the polymerizable monomer. The chain transfer agent may be copolymerized using the above-described intrinsic viscosity so that the intrinsic viscosity is 0.1 to 0.35. The chain transfer agent may be an α-methylstyrene dimer.
[0165]
Further, the thermoplastic resin composition of the present invention further has the above copolymer.reactionThe amount of the group is more than 0 and not more than 0.05 mol / kg with respect to the total amount of the rubber-reinforced styrene resin, the polymer and the copolymer.
[0166]
The thermoplastic resin composition of the present invention is further configured to have a molecular weight distribution defined by weight average molecular weight / number average molecular weight of 3 or less in the copolymer.
[0167]
According to the above configuration, the thermoplastic resin composition according to the present invention comprises a rubber-reinforced styrene resin and a so-called engineering plastic polymer (at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, and an amino group). As a compatibilizing agent for compatibilizing a polymer having at least one polymer selected from the group consisting of thermoplastic polyester, polyamide, and polycarbonate, and a crystalline polymer) By including the coalescence, the amount of the compatibilizer used for improving the impact resistance can be reduced (exceeding 0 to 0.05 mol / kg or less).
[0168]
For this reason, in the above configuration, it is possible to suppress a decrease in fluidity of each resin composition and sufficiently improve impact resistance without deteriorating physical properties such as heat resistance, solvent resistance, and workability. Can be made.
[0169]
In addition, when the molecular weight distribution defined by the weight average molecular weight / number average molecular weight in the copolymer is 3 or less, a decrease in fluidity of each resin composition can be further suppressed, and heat resistance can be reduced. The impact resistance can be sufficiently improved without deteriorating physical properties such as solvent resistance and workability.
[0170]
Thereby, in the said structure, while being excellent in impact resistance, it can be set as the thermoplastic resin composition with which physical properties, such as heat resistance, solvent resistance, and workability, and impact resistance were balanced. That is, the thermoplastic resin composition according to the present invention is excellent in impact resistance and also has the effect of excellent balance between physical properties such as heat resistance, solvent resistance, and workability and impact resistance. .

Claims (7)

Rubber reinforced styrene resin,
At least one polymer selected from the group consisting of thermoplastic polyester, polyamide and polycarbonate ;
Containing a copolymer having an oxazoline group as a reactive group in the molecule;
The thermoplastic resin composition intrinsic viscosity of the copolymer is characterized by 0.1 to 0.35 der Rukoto. 2. The thermoplastic resin composition according to claim 1, wherein an amount of the polymerizable monomer having an oxazoline group in the copolymer is in a range of 0.1 wt% to 20 wt% . The amount of reactive groups of the copolymer is more than 0 and not more than 0.05 mol / kg with respect to the total amount of the rubber-reinforced styrenic resin, the polymer and the copolymer. 2. The thermoplastic resin composition according to 2. The thermoplastic resin composition according to claim 1, 2 or 3, wherein the copolymer has a molecular weight distribution defined by weight average molecular weight / number average molecular weight of 3 or less. The thermoplastic resin composition according to claim 4, wherein the molecular weight distribution is 2 to 2.5 . The copolymer comprises a polymerizable monomer having a reactive group that reacts with a functional group of the polymer and a vinyl monomer copolymerizable with the polymerizable monomer, having an intrinsic viscosity of 0.1 to 0.35. The thermoplastic resin composition according to any one of claims 1 to 5, wherein a chain transfer agent is copolymerized so as to adjust the intrinsic viscosity. The thermoplastic resin composition according to claim 6, wherein the chain transfer agent is α-methylstyrene dimer.