JP2005023095A - Polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin composition having mechanical properties, especially flexibility and impact resistance under a low-temperature atmosphere such as -40°C and even excellent fluidity, moldability and chemical resistance. <P>SOLUTION: The polyester resin composition comprises (a) 95-60 wt.% of a polyester resin having 30-80 equivalents/t content of carboxy terminal groups and (b) 5-40 wt.% of an olefinic resin composed of (b-1) an olefin copolymer prepared by introducing a monomer component having an epoxy group into an olefinic polymer and (b-2) an ethylene/α-olefinic copolymer obtained by copolymerizing ethylene with a 3-20C α-olefin. The polyester resin composition has morphology in which (a) the polyester resin forms a continuous phase and (b) the olefinic resin is dispersed with 2-0.01 μm average particle diameter in the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００３５】
（Ｒは水素原子または低級アルキル基を示す）で示される化合物であり、具体的にはアクリル酸グリシジル、メタクリル酸グリシジルおよびエタクリル酸グリシジルなどが挙げられるが、中でもメタクリル酸グリシジルが好ましく使用される。 α−オレフィンとα，β−不飽和カルボン酸のグリシジルエステルを必須共重合成分とするオレフィン系共重合体の具体例としては、エチレン／プロピレン−ｇ−メタクリル酸グリシジル共重合体（”ｇ”はグラフトを表す、以下同じ）、エチレン／ブテン−１−ｇ−メタクリル酸グリシジル共重合体、エチレン／アクリル酸グリシジル共重合体、エチレン／メタクリル酸グリシジル共重合体、エチレン／アクリル酸メチル／メタクリル酸グリシジル共重合体、エチレン／メタクリル酸メチル／メタクリル酸グリシジル共重合体が挙げられる。中でも、エチレン／メタクリル酸グリシジル共重合体、エチレン／アクリル酸メチル／メタクリル酸グリシジル共重合体、エチレン／メタクリル酸メチル／メタクリル酸グリシジル共重合体が好ましく用いられる。
【００３６】
また、本発明で特に有用な（ｂ−２）エチレンと炭素数３〜２０のα−オレフィンからなるエチレン・α−オレフィン系共重合体は、エチレンおよび炭素数３〜２０を有する少なくとも１種以上のα−オレフィンを構成成分とする共重合体である。上記の炭素数３〜２０のα−オレフィンとして、具体的にはプロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、１−ヘプタデセン、１−オクタデセン、１−ノナデセン、１−エイコセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、３−エチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ヘキセン、 ４，４−ジメチル−１−ペンテン、４−エチル−１−ヘキセン、３−エチル−１−ヘキセン、９−メチル−１−デセン、１１−メチル−１−ドデセン、１２−エチル−１−テトラデセンおよびこれらの組み合わせが挙げられる。これらα−オレフィンの中でも炭素数６から１２であるα−オレフィンを用いた共重合体が衝撃強度の向上、改質効果の一層の向上が見られるためより好ましい。
【００３７】
本発明に用いる（ｂ）オレフィン系樹脂のメルトフローレート（以下ＭＦＲと略す。：ＡＳＴＭ Ｄ １２３８、１９０℃、２１６０ｇ荷重にて測定）は０．０１〜７０ｇ／１０分であることが好ましく、さらに好ましくは０．０３〜６０ｇ／１０分である。ＭＦＲが０．０１ｇ／１０分未満の場合は流動性が悪く、７０ｇ／１０分を超える場合は成形品の形状によっては衝撃強度が低くなる場合もあるので注意が必要である。
【００３８】
本発明に用いる（ｂ）オレフィン系樹脂の製造方法については特に制限はなく、ラジカル重合、チーグラー・ナッタ触媒を用いた配位重合、アニオン重合、メタロセン触媒を用いた配位重合などいずれの方法でも用いることができる。
【００３９】
本発明の（ａ）ポリエステル樹脂と（ｂ）オレフィン系樹脂の配合割合は、ポリエステル樹脂９５〜６０重量％、オレフィン系樹脂５〜４０重量％であり、好ましくは、ポリエステル樹脂８５〜７０重量％、オレフィン系樹脂１５〜３０重量％である。オレフィン系樹脂が５重量％より小さすぎると柔軟性及び耐衝撃性の改良効果が得にくく、逆に、４０重量％より多すぎるとポリエステル樹脂本来の熱安定性、耐薬品性が損なわれるばかりでなく、溶融混練時の増粘が大きくなるため、好ましくない。
【００４０】
更に、本発明においては、上記の如く（ｂ−１）エポキシ基含有オレフィン系共重合体と（ｂ−２）エチレン・α−オレフィン系共重合体を併用して用いることが好ましく、その併用割合は、両者の合計に対し、（ｂ−１）成分が５〜４０重量％、（ｂ−２）成分が９５〜６０重量％であり、好ましくは（ｂ−１）成分が１０〜３０重量％、（ｂ−２）成分が９０〜７０重量％である。（ｂ−１）成分が、５重量％より小さすぎると低温特性が得られにくい傾向にあり、また、４０重量％より多すぎると溶融混練時の増粘が大きくなり流動性が悪化する傾向にある。
【００４１】
本発明においては、低温時の靱性および耐衝撃性を損なわず、かつさらに耐薬品性の改良および加工時の流動性などの特性を付与する点から（ｃ）ポリフェニレンスルフィド樹脂（以下ＰＰＳと略す）を含有せしめることが必要である。
【００４２】
本発明に用いる（ｃ）ＰＰＳは、下記構造式で示される繰り返し単位を有する重合体であり、
【００４３】
【化２】

【００４４】
耐熱性の観点からは前記構造式で示される繰り返し単位を７０モル％以上、更には９０モル％以上含む重合体が好ましい。またＰＰＳはその繰り返し単位の３０モル％未満程度が、下記の構造を有する繰り返し単位等で構成されていてもよい。
なかでもｐ−フェニレンスルフィド／ｍ−フェニレンスルフィド共重合体（ｍ−フェニレンスルフィド単位２０％以下）などは成形加工性とバリア性を兼備する点で好ましく用いられ得る。
【００４５】
【化３】

【００４６】
かかるＰＰＳは通常公知のポリハロゲン芳香族化合物とスルフィド化剤とを極性有機溶媒中で反応させて得られるＰＰＳを回収、後処理することで高収率で製造することができ、具体的には特公昭４５−３３６８号公報に記載される比較的分子量の小さな重合体を得る方法、あるいは特公昭５２−１２２４０号公報や特開昭６１−７３３２号公報に記載される比較的分子量の大きな重合体を得る方法などによっても製造できるが、本発明において前記の様に得られたＰＰＳを空気中加熱による架橋／高分子量化、窒素などの不活性ガス雰囲気下あるいは減圧下での熱処理、有機溶媒、熱水、酸水溶液などによる洗浄、酸無水物、アミン、イソシアネート、官能基含有ジスルフィド化合物などの官能基含有化合物による活性化など種々の処理を施した上で使用することが好ましい。
【００４７】
ＰＰＳの加熱による架橋／高分子量化する場合の具体的方法としては、空気、酸素などの酸化性ガス雰囲気下あるいは前記酸化性ガスと窒素、アルゴンなどの不活性ガスとの混合ガス雰囲気下で、加熱容器中で所定の温度において希望する溶融粘度が得られるまで加熱を行う方法が例示できる。加熱処理温度は通常、１７０〜２８０℃が選択され、好ましくは２００〜２７０℃である。また、加熱処理時間は通常０．５〜１００時間が選択され、好ましくは２〜５０時間であるが、この両者をコントロールすることにより目標とする粘度レベルを得ることができる。加熱処理の装置は通常の熱風乾燥機でもまた回転式あるいは撹拌翼付の加熱装置であってもよいが、効率よくしかもより均一に処理ためには回転式あるいは撹拌翼付の加熱装置を用いるのがより好ましい。
【００４８】
ＰＰＳを窒素などの不活性ガス雰囲気下あるいは減圧下で熱処理する場合の具体的方法としては、窒素などの不活性ガス雰囲気下あるいは減圧下で、加熱処理温度１５０〜２８０℃、好ましくは２００〜２７０℃、加熱時間は０．５〜１００時間、好ましくは２〜５０時間加熱処理する方法が例示できる。加熱処理の装置は、通常の熱風乾燥機でもまた回転式あるいは撹拌翼付の加熱装置であってもよいが、効率よくしかもより均一に処理するためには回転式あるいは撹拌翼付の加熱装置を用いるのがより好ましい。
【００４９】
本発明で用いられる（ｃ）ＰＰＳは脱イオン処理を施されたＰＰＳであることが好ましい。かかる脱イオン処理の具体的方法としては酸水溶液洗浄処理、熱水洗浄処理および有機溶媒洗浄処理などが例示でき、これらの処理は２種以上の方法を組み合わせて用いても良い。
【００５０】
ＰＰＳを有機溶媒で洗浄する場合の具体的方法としては以下の方法が例示できる。すなわち、洗浄に用いる有機溶媒としては、ＰＰＳを分解する作用などを有しないものであれば特に制限はないが、例えばＮ−メチルピロリドン、ジメチルホルムアミド、ジメチルアセトアミドなどの含窒素極性溶媒、ジメチルスルホキシド、ジメチルスルホンなどのスルホキシド、スルホン系溶媒、アセトン、メチルエチルケトン、ジエチルケトン、アセトフェノンなどのケトン系溶媒、ジメチルエーテル、ジプロピルエーテル、テトラヒドロフランなどのエーテル系溶媒、クロロホルム、塩化メチレン、トリクロロエチレン、２塩化エチレン、ジクロルエタン、テトラクロルエタン、クロルベンゼンなどのハロゲン系溶媒、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、エチレングリコール、プロピレングリコール、フェノール、クレゾール、ポリエチレングリコールなどのアルコール、フェノール系溶媒、ベンゼン、トルエン、キシレンなどの芳香族炭化水素系溶媒などがあげられる。これらの有機溶媒のなかでＮ−メチルピロリドン、アセトン、ジメチルホルムアミド、クロロホルムなどの使用が好ましい。また、これらの有機溶媒は、１種類または２種類以上を混合して使用される。有機溶媒による洗浄の方法としては、有機溶媒中にＰＰＳを浸漬せしめるなどの方法があり、必要により適宜撹拌または加熱することも可能である。有機溶媒でＰＰＳを洗浄する際の洗浄温度については特に制限はなく、常温〜３００℃程度の任意の温度が選択できる。洗浄温度が高くなるほど洗浄効率が高くなる傾向があるが、通常は常温〜１５０℃の洗浄温度で十分効果が得られる。また有機溶媒洗浄を施されたＰＰＳは残留している有機溶媒を除去するため、水または温水で数回洗浄することが好ましい。
【００５１】
ＰＰＳを熱水で洗浄処理する場合の具体的方法としては以下の方法が例示できる。すなわち熱水洗浄によるＰＰＳの好ましい化学的変性の効果を発現するため、使用する水は蒸留水あるいは脱イオン水であることが好ましい。熱水処理の操作は、通常、所定量の水に所定量のＰＰＳを投入し、常圧で或いは圧力容器内で加熱、撹拌することにより行われる。ＰＰＳと水との割合は、水の多いほうが好ましいが、通常、水１リットルに対し、ＰＰＳ２００ｇ以下の浴比が選択される。
【００５２】
ＰＰＳを酸水溶液で洗浄処理する場合の具体的方法としては以下の方法が例示できる。すなわち、酸または酸の水溶液にＰＰＳを浸漬せしめるなどの方法があり、必要により適宜撹拌または加熱することも可能である。用いられる酸はＰＰＳを分解する作用を有しないものであれば特に制限はなく、ギ酸、酢酸、プロピオン酸、酪酸などの脂肪族飽和モノカルボン酸、クロロ酢酸、ジクロロ酢酸などのハロ置換脂肪族飽和カルボン酸、アクリル酸、クロトン酸などの脂肪族不飽和モノカルボン酸、安息香酸、サリチル酸などの芳香族カルボン酸、シュウ酸、マロン酸、コハク酸、フタル酸、フマル酸などのジカルボン酸、硫酸、リン酸、塩酸、炭酸、珪酸などの無機酸性化合物などがあげられる。中でも酢酸、塩酸がより好ましく用いられる。酸処理を施されたＰＰＳは残留している酸または塩などを除去するために、水または温水で数回洗浄することが好ましい。また洗浄に用いる水は、酸処理によるＰＰＳの好ましい化学的変性の効果を損なわない意味で蒸留水あるいは脱イオン水であることが好ましい。
【００５３】
本発明で用いられる（ｃ）ＰＰＳの溶融粘度は、溶融混練が可能であれば特に制限はないが、通常５〜２０００Ｐａ・ｓ（３２０℃、剪断速度１０００ｓｅｃ−^１）のものが使用され、１０〜５００Ｐａ・ｓの範囲がより好ましい。ここで溶融粘度は、剪断速度１０００ｓｅｃ−^１の条件下でノズル径０．５ｍｍφ、ノズル長１０ｍｍのノズルを用い高化式フローテスターによって測定した値である。
【００５４】
本発明で用いられる（ｃ）ＰＰＳの（ａ）ポリエステル樹脂と（ｂ）オレフィン系樹脂からなる組成物への配合量は、低温時の靱性および耐衝撃性を損なわず、かつさらに耐薬品性の改良および加工時の流動性などの特性を付与する点から（ａ）および（ｂ）の合計１００重量部に対して１〜３０重量部であり、より好ましくは２〜２０重量部、特に好ましくは５〜１５重量部である。
【００５５】
また、本発明においては、低温時の靱性および耐衝撃性を損なわず、かつさらに耐薬品性の改良および加工時の流動性などの特性を付与する点から（ｄ）液晶性樹脂を含有せしめることが必要である。
【００５６】
本発明で用いられる（ｄ）液晶性樹脂は、異方性溶融相を形成し得る樹脂であり、エステル結合を有するものが好ましい。例えば芳香族オキシカルボニル単位、芳香族ジオキシ単位、芳香族および／または脂肪族ジカルボニル単位、アルキレンジオキシ単位などから選ばれた構造単位からなり、かつ異方性溶融相を形成する液晶性ポリエステル、あるいは、上記構造単位と芳香族イミノカルボニル単位、芳香族ジイミノ単位、芳香族イミノオキシ単位などから選ばれた構造単位からなり、かつ異方性溶融相を形成する液晶性ポリエステルアミドなどである。
【００５７】
芳香族オキシカルボニル単位としては、例えば、ｐ−ヒドロキシ安息香酸、６−ヒドロキシ−２−ナフトエ酸などから生成した構造単位、芳香族ジオキシ単位としては、例えば、４，４´−ジヒドロキシビフェニル、ハイドロキノン、３，３’，５，５’−テトラメチル−４，４’−ジヒドロキシビフェニル、ｔ−ブチルハイドロキノン、フェニルハイドロキノン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン、２，２−ビス（４−ヒドロキシフェニル）プロパンおよび４，４’−ジヒドロキシジフェニルエーテルなどから生成した構造単位、芳香族および／または脂肪族ジカルボニル単位としては、例えば、テレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、４，４’−ジフェニルジカルボン酸、１，２−ビス（フェノキシ）エタン−４，４’−ジカルボン酸、１，２−ビス（２−クロルフェノキシ）エタン−４，４’−ジカルボン酸および４，４’ジフェニルエーテルジカルボン酸、アジピン酸、セバシン酸などから生成した構造単位、アルキレンジオキシ単位としてはエチレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール等から生成した構造単位（なかでもエチレングリコールから生成した構造単位が好ましい。）、芳香族イミノオキシ単位としては、例えば、４−アミノフェノールなどから生成した構造単位が挙げられる。
【００５８】
液晶性ポリエステルの具体例としては、ｐ−ヒドロキシ安息香酸および６−ヒドロキシ−２−ナフトエ酸から生成した構造単位からなる液晶性ポリエステル、ｐ−ヒドロキシ安息香酸から生成した構造単位、６−ヒドロキシ−２−ナフトエ酸から生成した構造単位、芳香族ジヒドロキシ化合物および／または脂肪族ジカルボン酸から生成した構造単位からなる液晶性ポリエステル、ｐ−ヒドロキシ安息香酸から生成した構造単位、４，４’−ジヒドロキシビフェニルから生成した構造単位、テレフタル酸および／またはアジピン酸、セバシン酸等の脂肪族ジカルボン酸から生成した構造単位からなる液晶性ポリエステル、ｐ−ヒドロキシ安息香酸から生成した構造単位、エチレングリコールから生成した構造単位、テレフタル酸から生成した構造単位からなる液晶性ポリエステル、ｐ−ヒドロキシ安息香酸から生成した構造単位、エチレングリコールから生成した構造単位、テレフタル酸およびイソフタル酸から生成した構造単位からなる液晶性ポリエステル、ｐ−ヒドロキシ安息香酸から生成した構造単位、エチレングリコールから生成した構造単位、４，４’−ジヒドロキシビフェニルから生成した構造単位、テレフタル酸および／またはアジピン酸、セバシン酸等の脂肪族ジカルボンから生成した構造単位からなる液晶性ポリエステル、ｐ−ヒドロキシ安息香酸から生成した構造単位、エチレングリコールから生成した構造単位、芳香族ジヒドロキシ化合物から生成した構造単位、テレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸などの芳香族ジカルボン酸から生成した構造単位からなる液晶性ポリエステルなどが挙げられる。
【００５９】
なかでも異方性溶融相を形成する液晶性ポリエステルの例としては、下記一般式中に記載した（Ｉ）、（ＩＩ）、（ＩＩＩ）および（ＩＶ）の構造単位からなる液晶性ポリエステル、または、（Ｉ）、（ＩＩＩ） および（ＩＶ）の構造単位からなる液晶性ポリエステルなどが好ましく挙げられる。
【００６０】
特に好ましいのは（Ｉ）、（ＩＩ）、（ＩＩＩ）および（ＩＶ）の構造単位からなる液晶性ポリエステルである。
【００６１】
【化４】

【００６２】
（ただし式中のＲ_１は下記一般式から選ばれた１種以上の基を示す。ただし式中Ｘは水素原子または塩素原子を示す。）
【００６３】
【化５】

【００６４】
（ただし、Ｒ_２は下記一般式中から選ばれた１種以上の基を示す。ただし式中Ｘは水素原子または塩素原子を示す。）
【００６５】
【化６】

【００６６】
上記構造単位（Ｉ）はｐ−ヒドロキシ安息香酸から生成した構造単位であり、構造単位（ＩＩ）は４，４’−ジヒドロキシビフェニル、３，３’，５，５’−テトラメチル−４，４’−ジヒドロキシビフェニル、ハイドロキノン、ｔ−ブチルハイドロキノン、フェニルハイドロキノン、メチルハイドロキノン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン、２，２−ビス（４−ヒドロキシフェニル）プロパンおよび４，４’−ジヒドロキシジフェニルエーテルから選ばれた一種以上の芳香族ジヒドロキシ化合物から生成した構造単位を、構造単位（ＩＩＩ）はエチレングリコールから生成した構造単位を、構造単位（ＩＶ）はテレフタル酸、イソフタル酸、４，４’−ジフェニルジカルボン酸、２，６−ナフタレンジカルボン酸、１，２−ビス（フェノキシ）エタン−４，４’−ジカルボン酸、１，２−ビス（２−クロルフェノキシ）エタン−４，４’−ジカルボン酸および４，４’−ジフェニルエーテルジカルボン酸から選ばれた一種以上の芳香族ジカルボン酸から生成した構造単位を各々示す。これらのうちＲ_１が下記式
【００６７】
【化７】

【００６８】
であり、Ｒ_２が下記式
【００６９】
【化８】

【００７０】
であるものが特に好ましい。
【００７１】
本発明に好ましく使用できる液晶性ポリエステルは、上記したように、構造単位（Ｉ）、（ＩＩＩ）、（ＩＶ）からなる共重合体および上記構造単位（Ｉ）、（ＩＩ）、（ＩＩＩ）、（ＩＶ）からなる共重合体から選択される１種以上であり、上記構造単位（Ｉ）、（ＩＩ）、（ＩＩＩ）および（ＩＶ）の共重合量は任意である。しかし、本発明の特性を発揮させるためには次の共重合量であることが好ましい。
【００７２】
すなわち、上記構造単位（Ｉ）、（ＩＩ）、（ＩＩＩ）、（ＩＶ）からなる共重合体の場合は、上記構造単位（Ｉ）および（ＩＩ）の合計は構造単位（Ｉ）、（ＩＩ）および（ＩＩＩ）の合計に対して３０〜９５モル％が好ましく、特に４０〜８５モル％がより好ましい。また、構造単位（ＩＩＩ）は構造単位（Ｉ）、（ＩＩ）および（ＩＩＩ）の合計に対して７０〜５モル％が好ましく、特に６０〜１５モル％がより好ましい。また、構造単位（Ｉ）の（ＩＩ）に対するモル比［（Ｉ）／（ＩＩ）］は好ましくは７５／２５〜９５／５であり、より好ましくは７８／２２〜９３／７である。また、構造単位（ＩＶ）は構造単位（ＩＩ）および（ＩＩＩ）の合計と実質的に等モルであることが好ましい。
【００７３】
一方、上記構造単位（ＩＩ）を含まない場合は流動性の点から上記構造単位（Ｉ）は構造単位（Ｉ）および（ＩＩＩ）の合計に対して４０〜９０モル％であることが好ましく、６０〜８８モル％であることが特に好ましく、構造単位（ＩＶ）は構造単位（ＩＩＩ）と実質的に等モルであることが好ましい。
【００７４】
ここで実質的に等モルとは、末端を除くポリマー主鎖を構成するユニットが等モルであるが、末端を構成するユニットとしては必ずしも等モルとは限らないことを意味する。
【００７５】
また液晶性ポリエステルアミドとしては、上記構造単位（Ｉ）〜（ＩＶ）以外にｐ−アミノフェノールから生成したｐ−イミノフェノキシ単位を含有した異方性溶融相を形成するポリエステルアミドが好ましい。
【００７６】
上記好ましく用いることができる液晶性ポリエステル、液晶性ポリエステルアミドは、上記構造単位（Ｉ）〜（ＩＶ）を構成する成分以外に３，３’−ジフェニルジカルボン酸、２，２’−ジフェニルジカルボン酸などの芳香族ジカルボン酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジオン酸などの脂肪族ジカルボン酸、ヘキサヒドロテレフタル酸などの脂環式ジカルボン酸、クロルハイドロキノン、３，４’−ジヒドロキシビフェニル、４，４’−ジヒドロキシジフェニルスルホン、４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジヒドロキシベンゾフェノン、３，４’−ジヒドロキシビフェニル等の芳香族ジオール、プロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、１，４−シクロヘキサンジオール、１，４−シクロヘキサンジメタノール等の脂肪族、脂環式ジオールおよびｍ−ヒドロキシ安息香酸、２，６−ヒドロキシナフトエ酸などの芳香族ヒドロキシカルボン酸およびｐ−アミノ安息香酸などを液晶性を損なわない程度の範囲でさらに共重合せしめることができる。
【００７７】
本発明において使用する上記（ｄ）液晶性樹脂の製造方法は、特に制限がなく、公知のポリエステルの重縮合法に準じて製造できる。
【００７８】
例えば、上記液晶性ポリエステルの製造において、次の製造方法が好ましく挙げられる。
（１）ｐ−アセトキシ安息香酸および４，４’−ジアセトキシビフェニル、ジアセトキシベンゼンなどの芳香族ジヒドロキシ化合物のジアシル化物と２，６−ナフタレンジカルボン酸、テレフタル酸、イソフタル酸などの芳香族ジカルボン酸から脱酢酸縮重合反応によって液晶性ポリエステルを製造する方法。
（２）ｐ−ヒドロキシ安息香酸および４，４’−ジヒドロキシビフェニル、ハイドロキノンなどの芳香族ジヒドロキシ化合物と２，６−ナフタレンジカルボン酸、テレフタル酸、イソフタル酸などの芳香族ジカルボン酸に無水酢酸を反応させて、フェノール性水酸基をアシル化した後、脱酢酸重縮合反応によって液晶性ポリエステルを製造する方法。
（３）ｐ−ヒドロキシ安息香酸のフェニルエステルおよび４，４’−ジヒドロキシビフェニル、ハイドロキノンなどの芳香族ジヒドロキシ化合物と２，６−ナフタレンジカルボン酸、テレフタル酸、イソフタル酸などの芳香族ジカルボン酸のジフェニルエステルから脱フェノール重縮合反応により液晶性ポリエステルを製造する方法。
（４）ｐ−ヒドロキシ安息香酸および２，６−ナフタレンジカルボン酸、テレフタル酸、イソフタル酸などの芳香族ジカルボン酸に所定量のジフェニルカーボネートを反応させて、それぞれジフェニルエステルとした後、４，４’−ジヒドロキシビフェニル、ハイドロキノンなどの芳香族ジヒドロキシ化合物を加え、脱フェノール重縮合反応により液晶性ポリエステルを製造する方法。
（５）ポリエチレンテレフタレートなどのポリエステルのポリマー、オリゴマーまたはビス（β−ヒドロキシエチル）テレフタレートなど芳香族ジカルボン酸のビス（β−ヒドロキシエチル）エステルの存在下で（１）または（２）の方法により液晶性ポリエステルを製造する方法。
【００７９】
また、（ｄ）液晶性樹脂の溶融粘度は特に限定されないが、本発明の効果をより発揮するために、液晶性樹脂の融点＋１０℃で測定した値が、１００Ｐａ・ｓ以下であることが好ましく、より好ましくは０．１〜５０Ｐａ・ｓであり、最も好ましくは０．５〜３０Ｐａ・ｓである。なお、ここで溶融粘度は、剪断速度１０００ｓｅｃ−^１の条件下でノズル径０．５ｍｍφ、ノズル長１０ｍｍのノズルを用い高化式フローテスターによって測定した値である。
【００８０】
ここで、本件において融点とは示差熱量測定において、重合を完了したポリマーを室温から２０℃／分の昇温条件で測定した際に観測される吸熱ピーク温度（Ｔｍ１）の観測後、Ｔｍ１＋２０℃の温度で５分間保持した後、２０℃／分の降温条件で室温まで一旦冷却した後、再度２０℃／分の昇温条件で測定した際に観測される吸熱ピーク温度（Ｔｍ２）を融点とする。
【００８１】
本発明で用いられる（ｄ）液晶性樹脂の（ａ）ポリエステル樹脂と（ｂ）オレフィン系樹脂からなる組成物への配合量は、低温時の靱性および耐衝撃性を損なわず、かつさらに耐薬品性の改良および加工時の流動性などの特性を付与する点から（ａ）および（ｂ）の合計１００重量部に対して１〜３０重量部であり、より好ましくは２〜２０重量部、特に好ましくは５〜１５重量部である。
【００８２】
本発明のポリエステル樹脂組成物は、さらに以下に説明するような酸化防止剤あるいはその他の添加剤を配合することが可能である。
【００８３】
更に本発明においては、高い耐熱性及び熱安定性を保持するために、フェノール系、リン系化合物の中から選ばれた１種以上の酸化防止剤を含有せしめることが好ましい。かかる酸化防止剤の配合量は、耐熱改良効果の点から（ａ）および（ｂ）成分の合計１００重量部に対して、０．０１重量部以上、特に０．０２重量部以上であることが好ましく、成形時に発生するガス成分の観点からは、５重量部以下、特に１重量部以下であることが好ましい。また、フェノール系及びリン系酸化防止剤を併用して使用することは、特に耐熱性、熱安定性、流動性保持効果が大きく好ましい。
【００８４】
フェノール系酸化防止剤としては、ヒンダードフェノール系化合物が好ましく用いられ、具体例としては、トリエチレングリコール−ビス［３−ｔ−ブチル−（５−メチル−４−ヒドロキシフェニル）プロピオネート］、Ｎ、Ｎ’−ヘキサメチレンビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ヒドロシンナミド）、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン、ペンタエリスリチルテトラキス［３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］、１，３，５−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−ｓ−トリアジン−２，４，６−（１Ｈ，３Ｈ，５Ｈ）−トリオン、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、ｎ−オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−フェニル）プロピオネート、３，９−ビス［２−（３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ）−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、１，３，５−トリメチル−２，４，６−トリス−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼンなどが挙げられる。
【００８５】
中でも、エステル型高分子ヒンダードフェノールタイプが好ましく、具体的には、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン、ペンタエリスリチルテトラキス［３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］、３，９−ビス［２−（３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ）−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカンなどが好ましく用いられる。
【００８６】
次にリン系酸化防止剤としては、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリト−ル−ジ−ホスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリト−ル−ジ−ホスファイト、ビス（２，４−ジ−クミルフェニル）ペンタエリスリト−ル−ジ−ホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビスフェニレンホスファイト、ジ−ステアリルペンタエリスリトール−ジ−ホスファイト、トリフェニルホスファイト、３，５−ジーブチル−４−ヒドロキシベンジルホスフォネートジエチルエステルなどが挙げられる。
【００８７】
中でも、ポリエステル樹脂のコンパウンド中に酸化防止剤の揮発や分解を少なくするために、酸化防止剤の融点が高いものが好ましく、具体的にはビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリト−ル−ジ−ホスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリト−ル−ジ−ホスファイト、ビス（２，４−ジ−クミルフェニル）ペンタエリスリトール−ジ−ホスファイトなどが好ましく用いられる。
【００８８】
さらに、本発明のポリエステル樹脂組成物には本発明の効果を損なわない範囲において、オレフィン系樹脂以外の樹脂を添加することが可能である。例えば、結晶性の高い熱可塑性樹脂を少量添加することにより成形性を改良することが可能である。但し、この量が組成物全体３０重量％を超えるとポリエステル樹脂本来の特徴が損なわれるため好ましくなく、特に２０重量％以下の添加が好ましく使用される。熱可塑性樹脂の具体例としては、ポリアミド樹脂、変性ポリフェニレンエーテル樹脂、ポリサルフォン樹脂、ポリアリルサルフォン樹脂、ポリケトン樹脂、ポリエーテルイミド樹脂、ポリアリレート樹脂、ポリエーテルサルフォン樹脂、ポリエーテルケトン樹脂、ポリチオエーテルケトン樹脂、ポリエーテルエーテルケトン樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、四フッ化ポリエチレン樹脂などが挙げられる。また、改質を目的として、以下のような化合物の添加が可能である。イソシアネート系化合物、有機シラン系化合物、有機チタネート系化合物、有機ボラン系化合物、エポキシ化合物などのカップリング剤、ポリアルキレンオキサイドオリゴマ系化合物、チオエーテル系化合物、エステル系化合物、有機リン系化合物などの可塑剤、タルク、カオリン、有機リン化合物、ポリエーテルエーテルケトンなどの結晶核剤、モンタン酸ワックス類、ステアリン酸リチウム、ステアリン酸アルミ等の金属石鹸、エチレンジアミン・ステアリン酸・セバシン酸重宿合物、シリコーン系化合物などの離型剤、次亜リン酸塩などの着色防止剤、その他、滑剤、紫外線防止剤、着色剤、難燃剤、発泡剤などの通常の添加剤を配合することができる。上記化合物は何れも組成物全体の２０重量％を越えるとポリエステル樹脂本来の特性が損なわれるため好ましくなく、１０重量％以下、更に好ましくは１重量％以下の添加がよい。
【００８９】
本発明の方法により得られるポリエステル樹脂組成物には、本発明の効果を損なわない範囲で充填材を配合して使用することも可能である。かかる充填材の具体例としてはガラス繊維、炭素繊維、チタン酸カリウィスカ、酸化亜鉛ウィスカ、炭酸カルシウムウィスカー、ワラステナイトウィスカー、硼酸アルミウィスカ、アラミド繊維、アルミナ繊維、炭化珪素繊維、セラミック繊維、アスベスト繊維、石コウ繊維、金属繊維などの繊維状充填材、あるいはタルク、ワラステナイト、ゼオライト、セリサイト、マイカ、カオリン、クレー、パイロフィライト、ベントナイト、アスベスト、アルミナシリケートなどの珪酸塩、酸化珪素、酸化マグネシウム、アルミナ、酸化ジルコニウム、酸化チタン、酸化鉄などの金属化合物、炭酸カルシウム、炭酸マグネシウム、ドロマイトなどの炭酸塩、硫酸カルシウム、硫酸バリウムなどの硫酸塩、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウムなどの水酸化物、ガラスビーズ、ガラスフレーク、ガラス粉、セラミックビーズ、窒化ホウ素、炭化珪素、カーボンブラックおよびシリカ、黒鉛などの非繊維状充填材が用いられ、これらは中空であってもよく、さらにはこれら充填剤を２種類以上併用することも可能である。また、これらの充填材をイソシアネート系化合物、有機シラン系化合物、有機チタネート系化合物、有機ボラン系化合物およびエポキシ化合物などのカップリング剤で予備処理して使用してもよい。
【００９０】
本発明のポリエステル樹脂組成物は、低温での柔軟性及び耐衝撃性の高度バランスを得るために、図１に示したようにポリエステル樹脂１が連続相（マトリックス）を形成し、オレフィン系樹脂２が分散相を形成（海−島構造）し、かつ、分散相を形成するオレフィン系樹脂の平均粒子径が２〜０．０１μｍ、好ましくは１〜０．０１μｍで分散したモルホロジーとなることが必要である。ここで、本発明のモルホロジーは図１の形態に限定されるものではなく、オレフィン系樹脂粒子の形状が多角形、略楕円形などの非円形であってもかまわない。オレフィン系樹脂の分散が凝集形態となり、平均粒子径が２μｍより大きくなると低温特性が得られにくくなり、耐薬品性が低下する傾向となる。また、ポリエステルが連続相とならない場合には流動性や耐薬品性が低下する。本発明のモルホロジーである場合には低温特性に優れ、耐薬品性、流動性が特に優れる。
【００９１】
本発明のポリエステル樹脂組成物が上記モルホロジーを形成することにより、温度−４０℃の条件下、ＡＳＴＭ−Ｄ６３８に従って測定した引張り破断伸度２０〜４００％、かつＡＳＴＭ−Ｄ２５６に従って測定したノッチ付きアイゾット衝撃強度５００〜２０００Ｊ／ｍ、好ましくは引張り破断伸度３０〜４００％、ノッチ付きアイゾット衝撃強度６００〜２０００Ｊ／ｍを発現させることが可能となる。
【００９２】
ここでいう平均粒子径とは、ポリエステル樹脂の融点＋２０℃の成形温度でＡＳＴＭ１号ダンベル片を成形し、その中心部から０．１μｍ以下（約８０ｎｍ）の薄片をダンベル片の断面積方向に切削し、透過型電子顕微鏡（倍率：１万倍）で観察した際の任意の１００ヶのオレフィン系樹脂の分散部分について、まずそれぞれの最大径と最小径を測定して平均値を求め、その後それらの平均値を求めた数平均粒子径である。
【００９３】
本発明のポリエステル樹脂組成物の製造に用いる混練機は、単軸、２軸の押出機、バンパリーミキサー、ニーダー、及びミキシングロールなど通常公知の溶融混練機に供給してポリエステル樹脂の融点以上の加工温度で混練する方法などを代表例として挙げることができるが、本発明のモルホロジーおよびオレフィン系共重合体の粒径を上述の如くコントロールするためには、せん断力を比較的強くすることが必要であり、また、混練時の滞留時間を短くする必要がある。これらの条件を組み合わせることによってオレフィン系共重合体の凝集を防ぎつつ、ポリエステル樹脂を連続相とすることができるからである。具体的には、２軸押出機を使用して、混練温度をポリエステル樹脂の融点＋５〜２０℃とし、滞留時間を１〜５分にする。この際、原料の混合順序には特に制限はなく、全ての原材料を配合後上記の方法により溶融混練する方法、一部の原材料を配合後上記の方法により溶融混練し更に残りの原材料を配合し溶融混練する方法、あるいは一部の原材料を配合後単軸あるいは２軸の押出機により溶融混練中にサイドフィーダーを用いて残りの原材料を混合する方法など、いずれの方法を用いてもよい。また、少量添加剤成分については、他の成分を上記の方法などで混練しペレット化した後、成形前に添加して成形に供することも勿論可能である。
【００９４】
本発明のポリエステル樹脂組成物は、耐衝撃性と流動性が優れることから射出成形体用途に特に有用である。また該特徴を活かして、一般機器、自動車用のパイプ、ケース等の構造体、電気電子用の金属インサート成形物品などへの使用に特に適している。
【００９５】
【実施例】
以下に実施例を挙げて本発明を更に具体的に説明する。材料特性については下記の方法により行った。
【００９６】
［カルボキシル量］ｍ−クレゾール溶液をアルカリ溶液で電位差滴定して求めた。カルボキシル末端基量はポリマ１トン当りの末端基量で表した。
【００９７】
［モルホロジー観察］射出成形（住友重機社製ＳＧ７５Ｈ−ＭＩＶ、シリンダー温度２８０℃、金型温度１３０℃）によりＡＳＴＭ１号ダンベル片を成形し、その中心部から０．１μｍ以下の薄片を切削し、透過型電子顕微鏡で観察し、以下のように評価した。
○：図１記載のようにポリエステル樹脂が連続相形成場合。
×：図２のようにポリエステル樹脂とオレフィン系樹脂が共連続相形成場合。
【００９８】
［平均粒径］オレフィン系樹脂の平均粒子径の測定は、上記モルホロジー観察と同様に倍率１万倍で観察した射出成形品中の任意のオレフィン共重合体粒子１００ヶの分散部分について画像処理ソフト「Ｓｃｉｏｎ Ｉｍａｇｅ」を用いて、各々の粒子の最大径と最小径を測定して平均値を求め、その後それらの数平均値を求めた。
【００９９】
［成形下限圧］射出成形（住友重機社製ＳＧ７５Ｈ−ＭＩＶ、シリンダー温度２８０℃、金型温度１３０℃）により試験片を調製する際の最低充填圧力を求めた。
【０１００】
［−４０℃アイゾット衝撃強度］温度雰囲気を−４０℃にした以外はＡＳＴＭ−Ｄ２５６に従ってノッチ付きアイゾット衝撃強度を測定した。
【０１０１】
［−４０℃引張り破断伸度］温度雰囲気を−４０℃にした以外はＡＳＴＭ−Ｄ６３８に従って引張破断伸度を測定した。
【０１０２】
［耐薬品性］ＡＳＴＭ１号ダンベル片を６０℃×２４時間トルエン浸漬処理後のダンベル片表面を光学顕微鏡で観察し、表面荒れ（ボイド等）部分の有無を測定した。
◎：表面荒れ部分がほとんどなし。
○：表面荒れ部分が３０％以下。
△：表面荒れ部分が５０％程度。
×：表面荒れ部分１００％。
××：オレフィン系樹脂が溶出。
【０１０３】
［参考例１］ポリフェニレンスルフィド樹脂（Ｃ−１）の作製方法
撹拌機および底に弁の付いた２０リットルオートクレーブに、４７％水硫化ナトリウム（三協化成）２３８３ｇ（２０．０モル）、９６％水酸化ナトリウム８３１ｇ（１９．９モル）、Ｎ−メチル−２−ピロリドン（ＮＭＰ）３９６０ｇ（４０．０モル）、およびイオン交換水３０００ｇを仕込み、常圧で窒素を通じながら２２５℃まで約３時間かけて徐々に加熱し、水４２００ｇおよびＮＭＰ８０ｇを留出した後、反応容器を１６０℃に冷却した。仕込みアルカリ金属硫化物１モル当たりの系内残存水分量は０．１７モルであった。また、仕込みアルカリ金属硫化物１モル当たりの硫化水素の飛散量は０．０２１モルであった。
【０１０４】
次に、ｐ−ジクロロベンゼン（シグマアルドリッチ）２９４２ｇ（２０．０モル）、ＮＭＰ１５１５ｇ（１５．３モル）を加え、反応容器を窒素ガス下に密封した。その後、４００ｒｐｍで撹拌しながら、２００℃から２２７℃まで０．８℃／分の速度で昇温し、次いで２７４℃まで０．６℃／分の速度で昇温し、２７４℃で５０分保持した後、２８２℃まで昇温した。オートクレーブ底部の抜き出しバルブを開放し、窒素で加圧しながら、内容物を撹拌機付き容器に１５分かけてフラッシュし、２５０℃でしばらく撹拌して大半のＮＭＰを除去し、ポリフェニレンスルフィド（ＰＰＳ）と塩類を含む固形物を回収した。
【０１０５】
得られた固形物およびイオン交換水１５１２０ｇを撹拌機付きオートクレーブに入れ、７０℃で３０分洗浄した後、ガラスフィルターで吸引濾過した。次いで７０℃に加熱した１７２８０ｇのイオン交換水をガラスフィルターに注ぎ込み、吸引濾過してケークを得た。
【０１０６】
得られたケークおよびイオン交換水１１８８０ｇを、撹拌機付きオートクレーブに仕込み、オートクレーブ内部を窒素で置換した後、１９２℃まで昇温し、３０分保持した。その後オートクレーブを冷却して内容物を取り出した。
【０１０７】
内容物をガラスフィルターで吸引濾過した後、これに７０℃のイオン交換水１７２８０ｇを注ぎ込み吸引濾過してケークを得た。得られたケークを８０℃で熱風乾燥し、さらに１２０℃で２４時間で真空乾燥することにより、乾燥ＰＰＳを得た。得られたＰＰＳは、溶融粘度４０Ｐａ・ｓ（オリフィス０．５φ×１０ｍｍ、３２０℃、剪断速度１０００ｓｅｃ−^１）であった。
【０１０８】
［参考例２］液晶性樹脂（Ｄ−１）の作製方法
ｐ−ヒドロキシ安息香酸９０１重量部、４，４´−ジヒドロキシビフェニル１２６重量部、テレフタル酸１１２重量部、固有粘度が約０．６ｄｌ／ｇのポリエチレンテレフタレ−ト３４６重量部及び無水酢酸８８４重量部を撹拌翼、留出管を備えた反応容器に仕込み、重合を行った結果、芳香族オキシカルボニル単位７２．５モル当量、芳香族ジオキシ単位７．５モル当量、エチレンジオキシ単位２０モル当量、芳香族ジカルボン酸単位２７．５モル当量からなる融点２６５℃、２７５℃の溶融粘度１３Ｐａ・ｓ（オリフィス０．５φ×１０ｍｍ、剪断速度１０００ｓｅｃ−１）の液晶性樹脂が得られた。
【０１０９】
［実施例１〜７］、［比較例１〜６］
下に示す各成分を表１に記載の各割合でドライブレンドした後、日本製鋼所社製ＴＥＸ３０型２軸押出機で、シリンダー温度を２５０〜２８０℃に設定し、２００ｒｐｍのスクリュー回転にて溶融混練し、ストランドカッターによりペレット化した。１２０℃で１晩除湿乾燥したペレットを用い、射出成形（住友重機社製ＳＧ７５Ｈ−ＭＩＶ、シリンダー温度２８０℃、金型温度１３０℃）により試験片を調製した。また、表１に示すように必要に応じて酸化防止剤として下記のものを溶融混練時に添加した。各サンプルの低温特性およびモルホロジーなどを測定した結果は表１に示すとおりであった。本実施例が低温特性（柔軟性、耐衝撃性等）、流動性、耐薬品性等に優れるのに対し、比較例１〜３においては低温特性に劣り、比較例４〜５においては低温特性、流動性が共に劣るものであり、比較例６においては耐薬品性に劣るものであった。
【０１１０】
本実施例および比較例に用いた（ａ）ポリエステル樹脂は以下の通りである。（Ａ−１）：固有粘度０．５９、カルボキシル末端基量４９ｅｑ／ｔのポリエチレンテレフタレート樹脂。
（Ａ−２）：固有粘度０．６６、カルボキシル末端基量３８ｅｑ／ｔのポリエチレンテレフタレート樹脂。
（Ａ−３）：固有粘度０．７５、カルボキシル末端基量１３ｅｑ／ｔのポリエチレンテレフタレート樹脂。
（Ａ−４）：固有粘度０．７０、カルボキシル末端基量３５ｅｑ／ｔのポリブチレンテレフタレート樹脂。
（Ａ−５）：固有粘度０．６２、カルボキシル末端基量３３ｅｑ／ｔのポリエチレン−２，６−ナフタレンジカルボキシレート樹脂。
【０１１１】
同様に、（ｂ−１）オレフィン系樹脂は以下の通りである。
（Ｂ−１）：ＭＦＲ＝３ｇ／１０分（１９０℃、２．１６ｋｇ荷重）のエチレン／メタクリル酸グリシジル＝８８／１２（重量％）共重合体。
（Ｂ−２）：ＭＦＲ＝３ｇ／１０分（１９０℃、２．１６ｋｇ荷重）のエチレン／メタクリル酸グリシジル＝９４／６（重量％）共重合体。
【０１１２】
また、同様に（ｂ−２）オレフィン系樹脂は以下の通りである。
（Ｂ−３）： ＭＦＲ＝３．５ｇ／１０分（１９０℃、２．１６ｋｇ荷重）、密度０．８６４ｇ／ｃｍ^３のエチレン／１−ブテン共重合体。
（Ｂ−４）： ＭＦＲ＝０．５ｇ／１０分（１９０℃、２．１６ｋｇ荷重）、密度０．８６１ｇ／ｃｍ^３のエチレン／１−ブテン共重合体。
（Ｂ−５）： ＭＦＲ＝０．４ｇ／１０分（１９０℃、２．１６ｋｇ荷重）のエチレン／プロピレン＝８５／１５モル％共重合体。
【０１１３】
また、比較例として以下のオレフィン系樹脂を用いた。
（Ｂ−６）： 酸無水物変性されたエチレン／プロピレン＝８５／１５モル％共重合体。
【０１１４】
また、酸化防止剤として以下の２種類の化合物を用いた。
フェノール系：３，９−ビス［２−（３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ）−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン。
リン系：ビス（２，４−ジ−クミルフェニル）ペンタエリスリト−ル−ジ−ホスファイト。
【０１１５】
【表１】

【０１１６】
［実施例８〜１４］、［比較例７〜１２］
上記参考例１記載の（ｃ−１）ＰＰＳ成分および上記成分を表２で示す各割合でドライブレンドした後、日本製鋼所社製ＴＥＸ３０型２軸押出機で、シリンダー温度を２５０〜２８０℃に設定し、２００ｒｐｍのスクリュー回転にて溶融混練し、ストランドカッターによりペレット化した。１２０℃で１晩除湿乾燥したペレットを用い、射出成形（住友重機社製ＳＧ７５Ｈ−ＭＩＶ、シリンダー温度２８０℃、金型温度１３０℃）により試験片を調製した。各サンプルの低温特性およびモルホロジー、耐薬品性などを測定した結果は表２に示すとおりであった。本実施例が低温特性、流動性、耐薬品性等に優れるのに対し、比較例７〜９においては低温特性および耐薬品性に劣り、比較例１０においては低温特性、耐薬品性、流動性の全てにおいてに劣るものであり、比較例１１においては低温特性、流動性においてに劣るものであった。また、比較例１２においては耐薬品性に劣るものであった。
【０１１７】
【表２】

【０１１８】
［実施例１５〜２１］、［比較例１３〜１８］
参考例２記載の液晶樹脂（Ｄ−１）成分および上記記載の各成分を表３記載の各割合でドライブレンドした後、日本製鋼所社製ＴＥＸ３０型２軸押出機で、シリンダー温度を２５０〜２８０℃に設定し、２００ｒｐｍのスクリュー回転にて溶融混練し、ストランドカッターによりペレット化した。１２０℃で１晩除湿乾燥したペレットを用い、射出成形（住友重機社製ＳＧ７５Ｈ−ＭＩＶ、シリンダー温度２８０℃、金型温度１３０℃）により試験片を調製した。各サンプルの低温特性およびモルホロジー、耐薬品性などを測定した結果は表３に示すとおりであった。本実施例が低温特性、流動性、耐薬品性等に優れるのに対し、比較例１３〜１５においては低温特性および耐薬品性に劣り、比較例１６、１７においては低温特性、流動性においてに劣るものであり、また、比較例１８においては低温引張伸びと流動性に劣りポリエステル連続相が形成されず、耐薬品性にも劣った材料であった。
【０１１９】
【表３】

【０１２０】
【発明の効果】
本発明によれば、機械的性質、特に−４０℃もの低温雰囲気下で優れた柔軟性及び耐衝撃性を有し、かつ流動性や耐薬品性にも優れた射出成形に好適なポリエステル樹脂組成物が得られる。
【図面の簡単な説明】
【図１】ポリエステル樹脂が連続相を形成し、オレフィン系樹脂が分散した海−島構造のモデル図である。
【図２】ポリエステル樹脂とオレフィン系樹脂が共に連続相を形成した共連続相構造のモデル図である。
【符号の説明】
１ ポリエステル樹脂
２ オレフィン系樹脂[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester resin composition having mechanical properties, particularly excellent flexibility and impact resistance in a low temperature atmosphere of −40 ° C., and excellent chemical resistance and fluidity.
[0002]
[Prior art]
Polyester resins typified by polyethylene terephthalate and polybutylene terephthalate are used for various electric / electronic parts, machine parts and automobile parts because of their excellent characteristics.
[0003]
However, since polyester resins are inferior in impact resistance, particularly notched impact strength, many improvement methods have been conventionally proposed. Among them, monomers such as α-olefin and α, β-unsaturated glycidyl ester are proposed. For example, a method of blending a copolymer consisting of However, the molded products obtained by these methods show good impact resistance near room temperature, but there is a problem that impact resistance is greatly reduced, for example, in a low temperature atmosphere of about -40 ° C. In Patent Documents 1 and 2, a method of blending a specific glycidyl group-containing olefin copolymer and an ethylene / α-olefin copolymer, and in Patent Document 3, an ethylene / vinyl acetate copolymer is added to a specific polyester resin. A method of blending, Patent Document 4, discloses a means for improving impact resistance at low temperatures by a method of blending an impact-resistant component having an acid anhydride group and a specific glycidyl group-containing olefin copolymer. .
[0004]
[Patent Document 1]
Japanese Patent Publication No. 63-4466 (Claims)
[Patent Document 2]
JP 2002-206052 A (Claim 1)
[Patent Document 3]
Japanese Patent No. 3174339 (Claim 1)
[Patent Document 4]
JP-A-2002-234992 (Claim 1)
[0005]
[Problems to be solved by the invention]
However, in these conventionally proposed methods, a composition having an impact resistance of 500 J / m or more in a low temperature atmosphere has not been obtained, satisfying more advanced low temperature characteristics, and economical. In addition, the development of advantageous materials is also required. An object of the present invention is to obtain a polyester resin composition having flexibility and impact resistance in a low temperature atmosphere superior to conventional materials, and also excellent in fluidity and chemical resistance. .
[0006]
[Means for Solving the Problems]
Therefore, the present inventors have studied to solve the above problems, and as a result, by forming a specific morphology in a composition comprising (a) a polyester resin having a specific end group amount and (b) a specific olefin resin. The above problems have been solved, and it has been found that a remarkable effect can be obtained in chemical resistance, fluidity and the like by blending a polyphenylene sulfide resin or a liquid crystalline resin.
[0007]
That is, the present invention comprises the following items.
[0008]
(1) (a) 95 to 60% by weight of a polyester resin having a carboxyl end group amount of 30 to 80 eq / t, and (b-1) obtained by introducing a monomer component having an epoxy group into an olefin polymer. (B) Olefin-based resin consisting of an ethylene / α-olefin copolymer obtained by copolymerizing an olefin copolymer, (b-2) ethylene, and an α-olefin having 3 to 20 carbon atoms. % Of the resin composition, wherein (a) the polyester resin forms a continuous phase and (b) the olefin-based resin has a morphology in which the average particle size is 2 to 0.01 μm. A polyester resin composition.
[0009]
(2) (a) 95 to 60% by weight of a polyester resin having a carboxyl end group amount of 30 to 80 eq / t, and (b-1) obtained by introducing a monomer component having an epoxy group into an olefin polymer. (B) Olefin-based resin consisting of an ethylene / α-olefin copolymer obtained by copolymerizing an olefin copolymer, (b-2) ethylene, and an α-olefin having 3 to 20 carbon atoms. % (C) a resin composition containing 1 to 30 parts by weight of a polyphenylene sulfide resin, wherein (a) a polyester resin forms a continuous phase and (b) an olefin. A polyester resin composition having a morphology in which a system resin is dispersed in an average particle size of 2 to 0.01 μm in the composition.
[0010]
(3) (a) 95 to 60% by weight of a non-liquid crystalline polyester resin having a carboxyl end group amount of 30 to 80 eq / t, and (b-1) a monomer component having an epoxy group is introduced into the olefin polymer. And (b-2) an olefin resin 5 comprising an ethylene / α-olefin copolymer obtained by copolymerizing (b-2) ethylene and an α-olefin having 3 to 20 carbon atoms. (D) a resin composition containing 1 to 30 parts by weight of a liquid crystalline resin with respect to 100 parts by weight of a resin composition consisting of ˜40% by weight, wherein (a) the polyester resin forms a continuous phase ( b) A polyester resin composition characterized by having a morphology in which an olefinic resin is dispersed in the composition at an average particle size of 2 to 0.01 μm.
[0011]
(4) The tensile elongation at break of a molded product obtained by molding a polyester resin composition measured according to ASTM-D638 at a temperature of −40 ° C. is 20 to 400%, and the Izod impact strength measured according to ASTM-D256. It is 500-2000 J / m, The polyester resin composition in any one of said (1)-(3) characterized by the above-mentioned.
[0012]
(5) A molded article obtained by molding a polyester resin composition (a) having a carboxyl terminal group amount of 40 to 70 eq / t and a polyester resin composition measured according to ASTM-D638 at a temperature of -40 ° C. The polyester resin according to any one of (1) to (4) above, having an elongation at break of 30 to 400% and an Izod impact strength measured according to ASTM-D256 of 600 to 2000 J / m Composition.
[0013]
(6) The olefin copolymer obtained by introducing a monomer component having an epoxy group into the (b-1) olefin polymer is an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester. It is a copolymer, The polyester resin composition in any one of said (1)-(5) characterized by the above-mentioned.
[0014]
(7) The (a) polyester resin is at least one selected from polyethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate and copolymers thereof (1) to (1) (6) The polyester resin composition in any one.
[0015]
(8) The polyester resin composition as described in any one of (1) to (7) above, wherein an average particle size of the (b) olefin-based resin is 1 to 0.01 μm. Is to provide.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
The (a) polyester resin used in the present invention is a polymer having an ester bond in the main chain. Preferred examples include thermoplastic polyesters having an aromatic ring in the chain unit of the polymer. Specifically, usually, an aromatic dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof) and Examples thereof include a polymer or copolymer obtained by a condensation reaction mainly containing hydroxycarboxylic acid.
[0017]
Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl Examples include dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 5-sodium sulfoisophthalic acid and ester-forming derivatives thereof. Two or more of these aromatic dicarboxylic acids can be used in combination. Also used in combination with aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and their ester-forming derivatives You can also
[0018]
As the diol, an aliphatic diol having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, And cyclohexanedimethanol, cyclohexanediol, and the like, and ester-forming derivatives thereof. Two or more of these diols can be used in combination.
[0019]
Specific examples of the polyester preferably used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyalkylene terephthalate such as polyhexylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, Polybutylene-2,6-naphthalene dicarboxylate, polyethylene-1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polybutylene terephthalate / Decane dicarboxylate, poly (ethylene terephthalate / cyclohexanedimethylene terephthalate), polyethylene Non-liquid crystalline polyesters such as -4,4'-dicarboxylate / terephthalate and mixtures thereof. More preferable examples include polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalenedicarboxylate, and particularly preferable is polyethylene terephthalate, but these polyester resins have moldability, heat resistance, toughness, surface It is also practically suitable to use it as a mixture depending on necessary properties such as properties.
[0020]
The production method of the (a) polyester resin used in the present invention is not particularly limited, and is produced by a conventionally known direct polymerization method or transesterification method. The direct polymerization method referred to here is a method for producing a polyester resin by carrying out an esterification reaction with a dicarboxylic acid and a diol as main components, followed by a polycondensation reaction under reduced pressure. The transesterification method is a method for producing a polyester resin by carrying out an ester exchange reaction using an ester-forming derivative of a dicarboxylic acid and a diol as main components, followed by a polycondensation reaction under reduced pressure.
[0021]
When the direct polymerization method is used, an esterification reaction is first performed to form an oligomer, and then a polyester is produced by a polycondensation reaction. The method of this esterification reaction is not particularly limited, and may be a batch method or a continuous method, and the esterification conditions used for normal polyester production can be applied as they are. For example, the reaction temperature is 180 to 300 ° C. In particular, it is preferable to carry out under the condition of 200 to 280 ° C. Further, the reaction rate of the oligomer after the esterification reaction is preferably 97% or more.
[0022]
When the transesterification method is used, a polyester is produced by first performing an ester exchange reaction to obtain an oligomer and then performing a polycondensation reaction. The method of this transesterification is not particularly limited, and may be a batch method or a continuous method, and the transesterification conditions used for normal polyester production can be applied as they are. For example, the reaction temperature is 120 to 300 ° C. In particular, it is preferable to carry out under the condition of 140 to 280 ° C. Moreover, it is preferable that the reaction rate of the oligomer after transesterification is 80% or more.
[0023]
The oligomer obtained from the esterification reaction or transesterification reaction is then subjected to a polycondensation reaction, but the method is not particularly limited, and may be a batch method or a continuous method, and the polymerization conditions used for normal polyester production For example, the reaction temperature is 230 to 300 ° C., preferably 240 to 280 ° C., and the pressure is 667 Pa or less, preferably 133 Pa or less under reduced pressure.
[0024]
In addition, in order to obtain a polyester resin having a relatively large amount of carboxyl end groups used in the present invention of 30 to 80 eq / t (end group amount per ton of polymer), the polycondensation reaction time should be set longer than before. Is preferred.
[0025]
The (a) polyester resin used in the present invention has a carboxyl end group amount determined by potentiometric titration of an m-cresol solution with an alkaline solution, compared with 30 to 80 eq / t (end group amount per ton of polymer). It is necessary from the viewpoint of low temperature impact resistance. Preferably it is 35-75 eq / t, Most preferably, it is 40-70 eq / t. If the carboxyl end group amount is less than 30 eq / t, the fluidity is deteriorated and the low-temperature characteristics are deteriorated, and if it is more than 80 eq / t, hydrolysis is increased, which is not preferable.
[0026]
Although there is no restriction | limiting in the polymerization degree of these polyester resins, For example, the intrinsic viscosity measured at 25 degreeC in the 0.5% o-chlorophenol solution is the range of 0.35-2.00, More preferably, it is 0.00. A range of 50 to 1.50, particularly preferably 0.50 to 1.20 is preferable.
[0027]
Next, the (b) olefin resin used in the present invention requires that (b-1) an epoxy group-containing olefin copolymer and (b-2) an ethylene / α-olefin copolymer be used in combination. . Here, the (b-1) epoxy group-containing olefin copolymer used in the present invention is an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefin polymer.
[0028]
Examples of functional group-containing components for introducing an epoxy group-containing monomer component into an olefin polymer include epoxy groups such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid. The monomer containing is mentioned.
[0029]
The method for introducing these epoxy group-containing components is not particularly limited, and a method such as copolymerization with the α-olefin as described above or graft introduction to the olefin polymer using a radical initiator can be used.
[0030]
The introduction amount of the monomer component containing an epoxy group is suitably in the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol%, based on the entire epoxy group-containing olefin copolymer. It is.
[0031]
The (b-1) epoxy group-containing olefin copolymer particularly useful in the present invention is preferably an olefin copolymer having an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester as essential copolymerization components. Can be mentioned. As said alpha olefin, ethylene is mentioned preferably. These copolymers further include α, β-unsaturated carboxylic acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. It is also possible to copolymerize the alkyl ester and the like.
[0032]
In the present invention, it is particularly preferable to use an olefin-based copolymer containing an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid as essential components. Among them, 60 to 99% by weight of an α-olefin and α, β- An olefin copolymer having 1 to 40% by weight of an unsaturated carboxylic acid glycidyl ester as an essential copolymer component is particularly preferred.
[0033]
As the glycidyl ester of the α, β-unsaturated carboxylic acid,
[0034]
[Chemical 1]

[0035]
(R represents a hydrogen atom or a lower alkyl group). Specific examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably used. As a specific example of an olefin copolymer having an α-olefin and a glycidyl ester of α, β-unsaturated carboxylic acid as an essential copolymerization component, an ethylene / propylene-g-glycidyl methacrylate copolymer ("g" Represents graft, the same shall apply hereinafter), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate Examples include copolymers and ethylene / methyl methacrylate / glycidyl methacrylate copolymers. Of these, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, and ethylene / methyl methacrylate / glycidyl methacrylate copolymer are preferably used.
[0036]
In addition, (b-2) an ethylene / α-olefin copolymer comprising ethylene and an α-olefin having 3 to 20 carbon atoms, which is particularly useful in the present invention, is at least one or more having ethylene and 3 to 20 carbon atoms. It is a copolymer having the α-olefin as a constituent component. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1 -Pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl -1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and these See fit, and the like. Among these α-olefins, a copolymer using an α-olefin having 6 to 12 carbon atoms is more preferable because an improvement in impact strength and a further improvement in the reforming effect can be seen.
[0037]
The melt flow rate (hereinafter abbreviated as MFR) of (b) olefin resin used in the present invention is preferably 0.01 to 70 g / 10 min, as measured by ASTM D 1238, 190 ° C. and 2160 g load. Preferably it is 0.03-60g / 10min. When MFR is less than 0.01 g / 10 min, the fluidity is poor, and when it exceeds 70 g / 10 min, the impact strength may be lowered depending on the shape of the molded product, so care must be taken.
[0038]
There are no particular restrictions on the method for producing the (b) olefin resin used in the present invention, and any method such as radical polymerization, coordination polymerization using a Ziegler-Natta catalyst, anionic polymerization, or coordination polymerization using a metallocene catalyst may be used. Can be used.
[0039]
The blending ratio of (a) polyester resin and (b) olefin resin of the present invention is 95 to 60% by weight of polyester resin and 5 to 40% by weight of olefin resin, preferably 85 to 70% by weight of polyester resin, The olefin resin is 15 to 30% by weight. If the olefinic resin is less than 5% by weight, it is difficult to obtain the effect of improving the flexibility and impact resistance. Conversely, if it is more than 40% by weight, the inherent thermal stability and chemical resistance of the polyester resin are impaired. In addition, the thickening at the time of melt-kneading increases, which is not preferable.
[0040]
Further, in the present invention, as described above, it is preferable to use (b-1) an epoxy group-containing olefin copolymer and (b-2) an ethylene / α-olefin copolymer in combination, and the combined ratio thereof. Is 5 to 40% by weight of component (b-1) and 95 to 60% by weight of component (b-2), preferably 10 to 30% by weight of component (b-1) , (B-2) component is 90 to 70% by weight. If the component (b-1) is less than 5% by weight, the low temperature characteristics tend to be difficult to obtain, and if it is more than 40% by weight, the viscosity during melt-kneading tends to increase and the fluidity tends to deteriorate. is there.
[0041]
In the present invention, (c) polyphenylene sulfide resin (hereinafter abbreviated as PPS) from the viewpoint of imparting properties such as improved chemical resistance and fluidity during processing without impairing toughness and impact resistance at low temperatures. It is necessary to contain.
[0042]
(C) PPS used in the present invention is a polymer having a repeating unit represented by the following structural formula,
[0043]
[Chemical 2]

[0044]
From the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the structural formula is preferable. Moreover, about 30 mol% or less of the repeating units of PPS may be composed of repeating units having the following structure.
Among these, p-phenylene sulfide / m-phenylene sulfide copolymer (m-phenylene sulfide unit 20% or less) can be preferably used in terms of having both moldability and barrier properties.
[0045]
[Chemical 3]

[0046]
Such PPS can be produced in a high yield by recovering PPS obtained by reacting a known polyhalogen aromatic compound and a sulfidizing agent in a polar organic solvent, and after-treatment, specifically, A method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or a polymer having a relatively large molecular weight described in JP-B-52-12240 and JP-A-61-7332 In the present invention, the PPS obtained as described above is crosslinked / polymerized by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, an organic solvent, Various treatments such as washing with hot water, aqueous acid solution, etc., activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates, functional group-containing disulfide compounds It is preferred to use in terms of the.
[0047]
As a specific method in the case of crosslinking / high molecular weight by heating PPS, in an oxidizing gas atmosphere such as air or oxygen or in a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon, An example is a method in which heating is performed until a desired melt viscosity is obtained at a predetermined temperature in a heating container. The heat treatment temperature is usually 170 to 280 ° C, preferably 200 to 270 ° C. The heat treatment time is usually selected from 0.5 to 100 hours, and preferably 2 to 50 hours. By controlling both, a target viscosity level can be obtained. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade, but a heating apparatus with a rotary or stirring blade is used for efficient and more uniform treatment. Is more preferable.
[0048]
A specific method for heat-treating PPS under an inert gas atmosphere such as nitrogen or under reduced pressure is a heat treatment temperature of 150 to 280 ° C., preferably 200 to 270 under an inert gas atmosphere such as nitrogen or under reduced pressure. C. and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours can be exemplified. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade, but a heating apparatus with a rotary or stirring blade is used for efficient and more uniform treatment. More preferably it is used.
[0049]
(C) PPS used in the present invention is preferably PPS that has been subjected to deionization treatment. Specific examples of such deionization treatment include acid aqueous solution washing treatment, hot water washing treatment, and organic solvent washing treatment, and these treatments may be used in combination of two or more methods.
[0050]
The following method can be illustrated as a specific method when PPS is washed with an organic solvent. That is, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing PPS. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, Sulfoxides such as dimethylsulfone, sulfone solvents, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane, Halogen solvents such as tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol , Phenol, cresol, alcohols such as polyethylene glycol, phenolic solvents, benzene, toluene, and aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is preferable. These organic solvents are used alone or in combination of two or more. As a method of washing with an organic solvent, there is a method of immersing PPS in an organic solvent, and it is possible to appropriately stir or heat as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning PPS with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. In addition, PPS that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.
[0051]
The following method can be illustrated as a specific method when the PPS is washed with hot water. That is, the water used is preferably distilled water or deionized water in order to exhibit a preferable chemical modification effect of PPS by hot water washing. The operation of the hot water treatment is usually performed by putting a predetermined amount of PPS into a predetermined amount of water and heating and stirring at normal pressure or in a pressure vessel. The ratio of PPS and water is preferably as much as possible, but usually a bath ratio of 200 g or less of PPS is selected per liter of water.
[0052]
The following method can be illustrated as a specific method when PPS is washed with an acid aqueous solution. That is, there is a method of immersing PPS in an acid or an acid aqueous solution, and stirring or heating can be appropriately performed as necessary. The acid used is not particularly limited as long as it does not have the action of decomposing PPS, and is saturated with aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted aliphatic saturated such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acids such as carboxylic acid, acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid, sulfuric acid, Examples include inorganic acidic compounds such as phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Of these, acetic acid and hydrochloric acid are more preferably used. The acid-treated PPS is preferably washed several times with water or warm water in order to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the preferable chemical modification effect of PPS by acid treatment.
[0053]
The melt viscosity of (c) PPS used in the present invention is not particularly limited as long as melt kneading is possible, but usually 5 to 2000 Pa · s (320 ° C., shear rate 1000 sec− ¹ ) Are used, and the range of 10 to 500 Pa · s is more preferable. Here, the melt viscosity is a shear rate of 1000 sec- ¹ It is the value measured by the Koka type flow tester using a nozzle with a nozzle diameter of 0.5 mmφ and a nozzle length of 10 mm under the conditions.
[0054]
The amount of (c) PPS used in the present invention to the composition comprising (a) polyester resin and (b) olefin resin does not impair toughness and impact resistance at low temperatures, and further has chemical resistance. 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, and particularly preferably 2 to 20 parts by weight with respect to a total of 100 parts by weight of (a) and (b) in terms of imparting characteristics such as improvement and fluidity during processing. 5 to 15 parts by weight.
[0055]
Further, in the present invention, (d) a liquid crystalline resin is contained from the viewpoint of imparting characteristics such as improved chemical resistance and fluidity during processing without impairing toughness and impact resistance at low temperatures. is required.
[0056]
The liquid crystalline resin (d) used in the present invention is a resin that can form an anisotropic molten phase, and preferably has an ester bond. For example, a liquid crystalline polyester comprising a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, an alkylenedioxy unit, and the like, and forming an anisotropic melt phase, Alternatively, it is a liquid crystalline polyester amide comprising the structural unit and a structural unit selected from an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit, and the like, and forming an anisotropic melt phase.
[0057]
Examples of the aromatic oxycarbonyl unit include a structural unit generated from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and the like, and examples of the aromatic dioxy unit include 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4 Examples of structural units, aromatic and / or aliphatic dicarbonyl units generated from -hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl ether include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4 , 4′-Diphenyldicarboxylic acid, 1,2-bi Su (phenoxy) ethane-4,4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid and 4,4′diphenyl ether dicarboxylic acid, adipic acid, sebacic acid, etc. As the generated structural units and alkylenedioxy units, structural units generated from ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, etc. (in particular, structural units generated from ethylene glycol are preferred), aromatics. Examples of iminooxy units include structural units generated from 4-aminophenol and the like.
[0058]
Specific examples of the liquid crystalline polyester include a liquid crystalline polyester composed of a structural unit generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit generated from p-hydroxybenzoic acid, and 6-hydroxy-2. A structural unit generated from naphthoic acid, a liquid crystalline polyester composed of a structural unit generated from an aromatic dihydroxy compound and / or an aliphatic dicarboxylic acid, a structural unit generated from p-hydroxybenzoic acid, from 4,4′-dihydroxybiphenyl Generated structural units, liquid crystalline polyesters composed of structural units generated from aliphatic dicarboxylic acids such as terephthalic acid and / or adipic acid, sebacic acid, structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol , Structure produced from terephthalic acid Liquid crystalline polyester consisting of structural units, structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, liquid crystalline polyesters consisting of structural units generated from terephthalic acid and isophthalic acid, generated from p-hydroxybenzoic acid Liquid crystalline polyester comprising a structural unit generated from an ethylene diglycol, a structural unit generated from 4,4'-dihydroxybiphenyl, a structural unit generated from an aliphatic dicarboxylic such as terephthalic acid and / or adipic acid or sebacic acid From structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid Living Examples thereof include liquid crystalline polyesters composed of the formed structural units.
[0059]
Among them, examples of the liquid crystalline polyester that forms an anisotropic molten phase include liquid crystalline polyesters composed of structural units (I), (II), (III), and (IV) described in the following general formula, or Preferred examples thereof include liquid crystalline polyesters composed of structural units of (I), (III) and (IV).
[0060]
Particularly preferred are liquid crystalline polyesters comprising the structural units (I), (II), (III) and (IV).
[0061]
[Formula 4]

[0062]
(However, R in the formula ₁ Represents one or more groups selected from the following general formula. In the formula, X represents a hydrogen atom or a chlorine atom. )
[0063]
[Chemical formula 5]

[0064]
(However, R ₂ Represents one or more groups selected from the following general formula. In the formula, X represents a hydrogen atom or a chlorine atom. )
[0065]
[Chemical 6]

[0066]
The structural unit (I) is a structural unit generated from p-hydroxybenzoic acid, and the structural unit (II) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4. '-Dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'- A structural unit generated from one or more aromatic dihydroxy compounds selected from dihydroxydiphenyl ether, a structural unit (III) is a structural unit generated from ethylene glycol, a structural unit (IV) is terephthalic acid, isophthalic acid, 4, 4 '-Diphenyldicarboxylic acid, 2,6-naphthalene dicarboxylic acid 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid Each of the structural units generated from one or more aromatic dicarboxylic acids is shown. R of these ₁ Is the following formula
[0067]
[Chemical 7]

[0068]
And R ₂ Is the following formula
[0069]
[Chemical 8]

[0070]
Are particularly preferred.
[0071]
As described above, the liquid crystalline polyester that can be preferably used in the present invention includes a copolymer comprising the structural units (I), (III), and (IV) and the structural units (I), (II), (III), It is at least one selected from copolymers consisting of (IV), and the copolymerization amount of the structural units (I), (II), (III) and (IV) is arbitrary. However, in order to exhibit the characteristics of the present invention, the following copolymerization amount is preferable.
[0072]
That is, in the case of a copolymer comprising the structural units (I), (II), (III), and (IV), the sum of the structural units (I) and (II) is the structural units (I), (II ) And (III) is preferably 30 to 95 mol%, more preferably 40 to 85 mol%. Further, the structural unit (III) is preferably 70 to 5 mol%, more preferably 60 to 15 mol%, based on the total of the structural units (I), (II) and (III). The molar ratio [(I) / (II)] of structural unit (I) to (II) is preferably 75/25 to 95/5, more preferably 78/22 to 93/7. The structural unit (IV) is preferably substantially equimolar to the total of the structural units (II) and (III).
[0073]
On the other hand, when the structural unit (II) is not included, the structural unit (I) is preferably 40 to 90 mol% based on the total of the structural units (I) and (III) from the viewpoint of fluidity. It is particularly preferably 60 to 88 mol%, and the structural unit (IV) is preferably substantially equimolar to the structural unit (III).
[0074]
Here, “substantially equimolar” means that the unit constituting the polymer main chain excluding the terminal is equimolar, but the unit constituting the terminal is not necessarily equimolar.
[0075]
The liquid crystalline polyesteramide is preferably a polyesteramide that forms an anisotropic molten phase containing a p-iminophenoxy unit generated from p-aminophenol in addition to the structural units (I) to (IV).
[0076]
The liquid crystalline polyester and liquid crystalline polyester amide that can be preferably used include 3,3′-diphenyldicarboxylic acid, 2,2′-diphenyldicarboxylic acid and the like in addition to the components constituting the structural units (I) to (IV). Aromatic dicarboxylic acids, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and other aliphatic dicarboxylic acids, hexahydroterephthalic acid and other alicyclic dicarboxylic acids, chlorohydroquinone, 3,4'-dihydroxybiphenyl, 4, Aromatic diols such as 4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxybenzophenone, 3,4′-dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6 -Hexanediol, neopentyl glycol, Aliphatic, alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-aminobenzoic acid Etc. can be further copolymerized within a range not impairing the liquid crystallinity.
[0077]
There is no restriction | limiting in particular in the manufacturing method of said (d) liquid crystalline resin used in this invention, It can manufacture according to the well-known polyester polycondensation method.
[0078]
For example, in the production of the liquid crystalline polyester, the following production method is preferred.
(1) Diacylated products of aromatic dihydroxy compounds such as p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl and diacetoxybenzene, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by deacetic acid condensation polymerization reaction.
(2) Reaction of aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl and hydroquinone with aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid with acetic anhydride. Then, after acylating a phenolic hydroxyl group, a method for producing a liquid crystalline polyester by a deacetic acid polycondensation reaction.
(3) Phenyl ester of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid Of producing liquid crystalline polyester by dephenol polycondensation reaction.
(4) After reacting p-hydroxybenzoic acid and aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and the like with a predetermined amount of diphenyl carbonate to obtain diphenyl ester, 4,4 ′ A method for producing a liquid crystalline polyester by dephenol polycondensation reaction by adding an aromatic dihydroxy compound such as dihydroxybiphenyl or hydroquinone.
(5) Polyester polymer such as polyethylene terephthalate, oligomer or liquid crystal by the method of (1) or (2) in the presence of bis (β-hydroxyethyl) ester of aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate For producing a conductive polyester.
[0079]
Further, (d) the melt viscosity of the liquid crystalline resin is not particularly limited, but in order to further exert the effects of the present invention, the value measured at the melting point of the liquid crystalline resin + 10 ° C. is preferably 100 Pa · s or less. More preferably, it is 0.1-50 Pa * s, Most preferably, it is 0.5-30 Pa * s. Here, the melt viscosity is a shear rate of 1000 sec- ¹ It is the value measured by the Koka type flow tester using a nozzle with a nozzle diameter of 0.5 mmφ and a nozzle length of 10 mm under the conditions.
[0080]
Here, in this case, the melting point is a differential calorimetry. In the differential calorimetry, after observation of the endothermic peak temperature (Tm1) observed when the polymer having been polymerized is measured from room temperature under a temperature rising condition of 20 ° C./min, Tm1 + 20 ° C. After being held at temperature for 5 minutes, once cooled to room temperature under a temperature drop condition of 20 ° C./min, the endothermic peak temperature (Tm2) observed when measured again under a temperature rise condition of 20 ° C./min is defined as the melting point. .
[0081]
The blending amount of (d) liquid crystalline resin used in the present invention into the composition comprising (a) polyester resin and (b) olefin resin does not impair toughness and impact resistance at low temperature, and further has chemical resistance. 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, more preferably 2 to 20 parts by weight with respect to the total of 100 parts by weight of (a) and (b) from the viewpoint of imparting properties such as improvement in properties and fluidity during processing Preferably it is 5-15 weight part.
[0082]
The polyester resin composition of the present invention can further contain an antioxidant or other additives as described below.
[0083]
Furthermore, in the present invention, in order to maintain high heat resistance and thermal stability, it is preferable to include one or more antioxidants selected from phenolic and phosphorus compounds. The blending amount of the antioxidant is 0.01 parts by weight or more, particularly 0.02 parts by weight or more with respect to 100 parts by weight of the total of the components (a) and (b) from the viewpoint of heat resistance improvement effect. Preferably, from the viewpoint of the gas component generated during molding, it is preferably 5 parts by weight or less, particularly preferably 1 part by weight or less. In addition, the combined use of phenolic and phosphorus antioxidants is particularly preferable because of their large heat resistance, thermal stability and fluidity retention effect.
[0084]
As the phenolic antioxidant, a hindered phenolic compound is preferably used. Specific examples include triethylene glycol-bis [3-t-butyl- (5-methyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate ] Methane, pentaerythrityltetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl- 4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,1,3-tris (2-methyl-4-hydroxy) Cis-5-t-butylphenyl) butane, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), n-octadecyl-3- (3,5-di-t-butyl-4-hydroxy-) Phenyl) propionate, 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.
[0085]
Among them, ester type polymer hindered phenol type is preferable. Specifically, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, pentaerythrityl. Tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5- Methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane and the like are preferably used.
[0086]
Next, phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl). ) Pentaerythritol di-phosphite, bis (2,4-di-cumylphenyl) pentaerythritol di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-bisphenylene phosphite, di-stearyl pentaerythritol di-phosphite, triphenyl phosphite, 3,5-dibutyl-4-hydroxybenzyl phosphite Examples include phonate diethyl ester.
[0087]
Among them, in order to reduce the volatilization and decomposition of the antioxidant in the polyester resin compound, those having a high melting point of the antioxidant are preferable. Specifically, bis (2,6-di-t-butyl-4- Methylphenyl) pentaerythritol di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol -Di-phosphite is preferably used.
[0088]
Furthermore, it is possible to add a resin other than the olefin resin to the polyester resin composition of the present invention as long as the effects of the present invention are not impaired. For example, the moldability can be improved by adding a small amount of a highly crystalline thermoplastic resin. However, when this amount exceeds 30% by weight of the whole composition, the original characteristics of the polyester resin are impaired, and in particular, addition of 20% by weight or less is preferably used. Specific examples of thermoplastic resins include polyamide resins, modified polyphenylene ether resins, polysulfone resins, polyallyl sulfone resins, polyketone resins, polyetherimide resins, polyarylate resins, polyether sulfone resins, polyether ketone resins, poly Examples include thioether ketone resins, polyether ether ketone resins, polyimide resins, polyamideimide resins, and tetrafluoropolyethylene resins. Moreover, the following compounds can be added for the purpose of modification. Coupling agents such as isocyanate compounds, organosilane compounds, organotitanate compounds, organoborane compounds, epoxy compounds, polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, organophosphorus compounds, etc. , Talc, kaolin, organic phosphorus compound, crystal nucleating agent such as polyether ether ketone, montanic acid wax, metal soap such as lithium stearate, aluminum stearate, ethylenediamine / stearic acid / sebacic acid heavy compound, silicone Conventional additives such as release agents such as compounds, anti-coloring agents such as hypophosphite, and other lubricants, UV inhibitors, colorants, flame retardants, and foaming agents can be blended. If any of the above compounds exceeds 20% by weight of the total composition, the inherent properties of the polyester resin are impaired, and therefore it is not preferable, and it is preferable to add 10% by weight or less, more preferably 1% by weight or less.
[0089]
The polyester resin composition obtained by the method of the present invention can be used by blending a filler as long as the effects of the present invention are not impaired. Specific examples of such fillers include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, Fibrous fillers such as stone-brown fibers and metal fibers, or silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, magnesium oxide , Metal compounds such as alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, calcium hydroxide, magnesium hydroxide, water Non-fibrous fillers such as hydroxides such as aluminum fluoride, glass beads, glass flakes, glass powders, ceramic beads, boron nitride, silicon carbide, carbon black and silica, and graphite are used. It is also possible to use two or more kinds of these fillers in combination. These fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound.
[0090]
In the polyester resin composition of the present invention, in order to obtain a high balance between flexibility and impact resistance at low temperatures, the polyester resin 1 forms a continuous phase (matrix) as shown in FIG. Must form a dispersed phase (sea-island structure), and the olefinic resin forming the dispersed phase has an average particle size of 2 to 0.01 μm, preferably 1 to 0.01 μm. It is. Here, the morphology of the present invention is not limited to the form shown in FIG. 1, and the shape of the olefin resin particles may be non-circular such as a polygon or a substantially oval. When the dispersion of the olefin-based resin is in an agglomerated form and the average particle diameter is larger than 2 μm, low temperature characteristics are hardly obtained, and chemical resistance tends to be lowered. Moreover, when polyester does not become a continuous phase, fluidity | liquidity and chemical resistance will fall. In the case of the morphology of the present invention, the low temperature characteristics are excellent, and the chemical resistance and fluidity are particularly excellent.
[0091]
When the polyester resin composition of the present invention forms the above morphology, a notched Izod impact measured in accordance with ASTM-D256 and a tensile elongation at break of 20-400% measured according to ASTM-D638 under the condition of a temperature of −40 ° C. A strength of 500 to 2000 J / m, preferably a tensile elongation at break of 30 to 400%, and a notched Izod impact strength of 600 to 2000 J / m can be developed.
[0092]
The average particle size here refers to the molding of ASTM No. 1 dumbbell piece at a molding temperature of polyester resin melting point + 20 ° C., and a thin piece of 0.1 μm or less (about 80 nm) from the center is cut in the cross-sectional area direction of the dumbbell piece. Then, with respect to the dispersion portion of any 100 olefin-based resins observed with a transmission electron microscope (magnification: 10,000 times), first, the maximum diameter and the minimum diameter are measured and average values are obtained. It is the number average particle diameter for which the average value was obtained.
[0093]
The kneading machine used for the production of the polyester resin composition of the present invention is supplied to a generally known melt kneader such as a single-screw or twin-screw extruder, a bumper mixer, a kneader, and a mixing roll and has a melting point higher than that of the polyester resin. The method of kneading at the processing temperature can be given as a representative example, but in order to control the morphology of the present invention and the particle size of the olefin copolymer as described above, it is necessary to make the shearing force relatively strong. In addition, it is necessary to shorten the residence time during kneading. This is because by combining these conditions, the polyester resin can be made into a continuous phase while preventing aggregation of the olefin copolymer. Specifically, using a twin-screw extruder, the kneading temperature is set to the melting point of the polyester resin + 5 to 20 ° C., and the residence time is set to 1 to 5 minutes. At this time, the mixing order of the raw materials is not particularly limited, and a method in which all raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended. Any method such as a method of melt kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or biaxial extruder may be used. As for the small amount additive component, other components can be kneaded by the above-mentioned method and pelletized, then added before molding and used for molding.
[0094]
The polyester resin composition of the present invention is particularly useful for injection molded articles because of its excellent impact resistance and fluidity. Further, taking advantage of this feature, it is particularly suitable for use in general equipment, structures for automobiles, structures such as cases, and metal insert molded articles for electric and electronic use.
[0095]
【Example】
The present invention will be described more specifically with reference to the following examples. About the material characteristic, it carried out by the following method.
[0096]
[Carboxyl content] Determined by potentiometric titration of an m-cresol solution with an alkaline solution. The amount of carboxyl end groups was expressed as the amount of end groups per ton of polymer.
[0097]
[Morphological Observation] ASTM No. 1 dumbbell piece was formed by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C.), and a thin piece of 0.1 μm or less was cut from the center, and transmitted. It was observed with a scanning electron microscope and evaluated as follows.
○: When a polyester resin forms a continuous phase as shown in FIG.
X: When a polyester resin and an olefin resin form a co-continuous phase as shown in FIG.
[0098]
[Average particle diameter] The average particle diameter of the olefin-based resin is measured using image processing software for a dispersed portion of 100 arbitrary olefin copolymer particles in an injection-molded article observed at a magnification of 10,000 as in the above-described morphology observation. Using “Scion Image”, the maximum and minimum diameters of each particle were measured to determine the average value, and then the number average value was determined.
[0099]
[Molding Lower Limit Pressure] The minimum filling pressure when preparing a test piece by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C.) was determined.
[0100]
[−40 ° C. Izod Impact Strength] Notched Izod impact strength was measured according to ASTM-D256 except that the temperature atmosphere was −40 ° C.
[0101]
[−40 ° C. Tensile Breaking Elongation] The tensile breaking elongation was measured according to ASTM-D638 except that the temperature atmosphere was set to −40 ° C.
[0102]
[Chemical Resistance] The surface of a dumbbell piece after the ASTM No. 1 dumbbell piece was immersed in toluene at 60 ° C. for 24 hours was observed with an optical microscope, and the presence or absence of a rough surface portion (such as a void) was measured.
A: Almost no rough surface.
○: Surface rough portion is 30% or less.
(Triangle | delta): A rough surface part is about 50%.
X: Surface roughening part 100%.
XX: Olefin resin is eluted.
[0103]
[Reference Example 1] Method for producing polyphenylene sulfide resin (C-1)
In a 20 liter autoclave with a stirrer and a valve at the bottom, 2383 g (20.0 mol) of 47% sodium hydrosulfide (Sankyo Kasei), 831 g (19.9 mol) of 96% sodium hydroxide, N-methyl-2 -3960 g (40.0 mol) of pyrrolidone (NMP) and 3000 g of ion-exchanged water were charged, gradually heated to 225 ° C over about 3 hours while passing nitrogen at normal pressure, and after distilling 4200 g of water and 80 g of NMP, The reaction vessel was cooled to 160 ° C. The residual water content in the system per mole of the alkali metal sulfide charged was 0.17 mole. The amount of hydrogen sulfide scattered per mole of the alkali metal sulfide charged was 0.021 mol.
[0104]
Next, 2942 g (20.0 mol) of p-dichlorobenzene (Sigma Aldrich) and 1515 g (15.3 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas. Then, while stirring at 400 rpm, the temperature was increased from 200 ° C. to 227 ° C. at a rate of 0.8 ° C./min, then increased to 274 ° C. at a rate of 0.6 ° C./min, and held at 274 ° C. for 50 minutes. Then, the temperature was raised to 282 ° C. Open the extraction valve at the bottom of the autoclave, pressurize with nitrogen, flush the contents into a vessel with a stirrer over 15 minutes, stir at 250 ° C for a while to remove most of the NMP, polyphenylene sulfide (PPS) and Solids containing salts were collected.
[0105]
The obtained solid and 15120 g of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and suction filtered through a glass filter. Next, 17280 g of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake.
[0106]
The obtained cake and 11880 g of ion-exchanged water were charged into an autoclave equipped with a stirrer, and the inside of the autoclave was replaced with nitrogen, and then the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out.
[0107]
The contents were subjected to suction filtration with a glass filter, and then 17280 g of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake. The obtained cake was dried with hot air at 80 ° C., and further dried under vacuum at 120 ° C. for 24 hours to obtain dry PPS. The obtained PPS has a melt viscosity of 40 Pa · s (orifice 0.5φ × 10 mm, 320 ° C., shear rate 1000 sec- ¹ )Met.
[0108]
[Reference Example 2] Method for producing liquid crystalline resin (D-1)
901 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4′-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, 346 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, and 884 parts by weight of acetic anhydride Were charged into a reaction vessel equipped with a stirring blade and a distillation tube, and polymerization was performed. As a result, 72.5 molar equivalents of aromatic oxycarbonyl units, 7.5 molar equivalents of aromatic dioxy units, 20 molar equivalents of ethylenedioxy units, A liquid crystalline resin consisting of 27.5 molar equivalents of aromatic dicarboxylic acid units and having a melting point of 265 ° C. and 275 ° C. and a melt viscosity of 13 Pa · s (orifice 0.5φ × 10 mm, shear rate 1000 sec-1) was obtained.
[0109]
[Examples 1-7], [Comparative Examples 1-6]
After dry blending each component shown below in the proportions shown in Table 1, the cylinder temperature was set to 250 to 280 ° C. with a TEX30 twin screw extruder manufactured by Nippon Steel Works, and melted by rotating the screw at 200 rpm. It knead | mixed and pelletized with the strand cutter. A test piece was prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C.) using pellets dehumidified and dried at 120 ° C. overnight. Further, as shown in Table 1, the following substances were added as necessary during the melt kneading as needed. The results of measuring the low temperature characteristics and morphology of each sample are shown in Table 1. While this example is excellent in low temperature characteristics (flexibility, impact resistance, etc.), fluidity, chemical resistance, etc., Comparative Examples 1 to 3 are inferior to low temperature characteristics, and Comparative Examples 4 to 5 are low temperature characteristics. The fluidity was inferior, and in Comparative Example 6, the chemical resistance was inferior.
[0110]
The (a) polyester resin used in the examples and comparative examples is as follows. (A-1): Polyethylene terephthalate resin having an intrinsic viscosity of 0.59 and a carboxyl end group amount of 49 eq / t.
(A-2): Polyethylene terephthalate resin having an intrinsic viscosity of 0.66 and a carboxyl end group amount of 38 eq / t.
(A-3): Polyethylene terephthalate resin having an intrinsic viscosity of 0.75 and a carboxyl end group amount of 13 eq / t.
(A-4): Polybutylene terephthalate resin having an intrinsic viscosity of 0.70 and a carboxyl end group amount of 35 eq / t.
(A-5): Polyethylene-2,6-naphthalenedicarboxylate resin having an intrinsic viscosity of 0.62 and a carboxyl end group amount of 33 eq / t.
[0111]
Similarly, the (b-1) olefin resin is as follows.
(B-1): MFR = 3 g / 10 min (190 ° C., 2.16 kg load) ethylene / glycidyl methacrylate = 88/12 (% by weight) copolymer.
(B-2): MFR = 3 g / 10 min (190 ° C., 2.16 kg load) ethylene / glycidyl methacrylate = 94/6 (% by weight) copolymer.
[0112]
Similarly, the (b-2) olefin resin is as follows.
(B-3): MFR = 3.5 g / 10 min (190 ° C., 2.16 kg load), density 0.864 g / cm ³ Ethylene / 1-butene copolymer.
(B-4): MFR = 0.5 g / 10 min (190 ° C., 2.16 kg load), density 0.861 g / cm ³ Ethylene / 1-butene copolymer.
(B-5): MFR = 0.4 g / 10 min (190 ° C., 2.16 kg load) ethylene / propylene = 85/15 mol% copolymer.
[0113]
Moreover, the following olefin resin was used as a comparative example.
(B-6): Acid anhydride-modified ethylene / propylene = 85/15 mol% copolymer.
[0114]
Moreover, the following two types of compounds were used as antioxidants.
Phenol type: 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10- Tetraoxaspiro [5,5] undecane.
Phosphorus: Bis (2,4-di-cumylphenyl) pentaerythritol di-phosphite.
[0115]
[Table 1]

[0116]
[Examples 8 to 14], [Comparative Examples 7 to 12]
After dry blending the (c-1) PPS component and the component described in Reference Example 1 in the respective proportions shown in Table 2, the cylinder temperature was adjusted to 250 to 280 ° C. with a TEX30 twin screw extruder manufactured by Nippon Steel Works. It was set, melt kneaded with a screw rotation of 200 rpm, and pelletized with a strand cutter. A test piece was prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C.) using pellets dehumidified and dried at 120 ° C. overnight. The results of measuring the low temperature characteristics, morphology, chemical resistance, etc. of each sample are shown in Table 2. While this example is excellent in low-temperature characteristics, fluidity, chemical resistance, etc., Comparative Examples 7-9 are inferior in low-temperature characteristics and chemical resistance, and in Comparative Example 10, low-temperature characteristics, chemical resistance, fluidity. In Comparative Example 11, the low temperature characteristics and fluidity were inferior. In Comparative Example 12, the chemical resistance was inferior.
[0117]
[Table 2]

[0118]
[Examples 15 to 21], [Comparative Examples 13 to 18]
After dry blending the liquid crystal resin (D-1) component described in Reference Example 2 and each component described above at the respective ratios described in Table 3, the cylinder temperature was adjusted to 250 to 250 using a TEX30 twin screw extruder manufactured by Nippon Steel Works. It set to 280 degreeC, it melt-kneaded by the screw rotation of 200 rpm, and was pelletized with the strand cutter. A test piece was prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C.) using pellets dehumidified and dried at 120 ° C. overnight. The results of measuring the low temperature characteristics, morphology, chemical resistance, etc. of each sample are shown in Table 3. While this example is excellent in low temperature characteristics, fluidity, chemical resistance, etc., Comparative Examples 13 to 15 are inferior in low temperature characteristics and chemical resistance, and in Comparative Examples 16 and 17, in low temperature characteristics and fluidity. In Comparative Example 18, the material was inferior in low-temperature tensile elongation and fluidity, did not form a polyester continuous phase, and inferior in chemical resistance.
[0119]
[Table 3]

[0120]
【The invention's effect】
According to the present invention, a polyester resin composition suitable for injection molding having mechanical properties, particularly excellent flexibility and impact resistance under a low temperature atmosphere of −40 ° C., and excellent fluidity and chemical resistance. Things are obtained.
[Brief description of the drawings]
FIG. 1 is a model diagram of a sea-island structure in which a polyester resin forms a continuous phase and an olefin resin is dispersed.
FIG. 2 is a model diagram of a co-continuous phase structure in which a polyester resin and an olefin resin both form a continuous phase.
[Explanation of symbols]
1 Polyester resin
2 Olefin resin

Claims (8)

(A) 95 to 60% by weight of a polyester resin having a carboxyl end group amount of 30 to 80 eq / t, and (b-1) an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefin polymer. (B-2) consisting of an ethylene / α-olefin copolymer obtained by copolymerizing ethylene and (b-2) ethylene and an α-olefin having 3 to 20 carbon atoms (b) consisting of 5 to 40% by weight of an olefin resin A polyester resin, characterized in that (a) the polyester resin forms a continuous phase and (b) the olefin resin has a morphology in which the average particle diameter is 2 to 0.01 μm dispersed in the composition. Composition. (A) 95 to 60% by weight of a polyester resin having a carboxyl end group amount of 30 to 80 eq / t, and (b-1) an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefin polymer. And (b-2) an ethylene / α-olefin copolymer obtained by copolymerizing ethylene and (b-2) ethylene and an α-olefin having 3 to 20 carbon atoms. (C) a resin composition containing 1 to 30 parts by weight of a polyphenylene sulfide resin with respect to 100 parts by weight of the resin composition, wherein (a) a polyester resin forms a continuous phase and (b) an olefin-based resin A polyester resin composition characterized by having a morphology dispersed in an average particle diameter of 2 to 0.01 μm in the composition. (A) 95 to 60% by weight of a non-liquid crystalline polyester resin having a carboxyl end group amount of 30 to 80 eq / t, and (b-1) an olefin polymer obtained by introducing a monomer component having an epoxy group. (B) Olefin-based resin consisting of an ethylene / α-olefin copolymer obtained by copolymerizing an olefin copolymer, (b-2) ethylene, and an α-olefin having 3 to 20 carbon atoms. % (D) 1-30 parts by weight of a liquid crystalline resin, (a) a polyester resin forms a continuous phase, and (b) an olefin. A polyester resin composition characterized by having a morphology in which a resin is dispersed with an average particle diameter of 2 to 0.01 μm in the composition. A molded article formed by molding a polyester resin composition measured according to ASTM-D638 at a temperature of −40 ° C. has a tensile elongation at break of 20 to 400% and an Izod impact strength measured according to ASTM-D256 of 500 to 2000 J. It is / m, The polyester resin composition in any one of Claims 1-3 characterized by the above-mentioned. (A) The amount of carboxyl terminal groups of the polyester resin is 40 to 70 eq / t, and the tensile break elongation of a molded product formed by molding a polyester resin composition measured according to ASTM-D638 at a temperature of −40 ° C. The polyester resin composition according to claim 1, wherein the polyester resin composition has a degree of 30 to 400% and an Izod impact strength measured according to ASTM-D256 of 600 to 2000 J / m. The (b-1) olefin copolymer obtained by introducing a monomer component having an epoxy group into the olefin polymer is a copolymer of an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester. The polyester resin composition according to claim 1, wherein the composition is a polyester resin composition. The polyester resin (a) is at least one selected from polyethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, and copolymers thereof. The polyester resin composition as described in 2. The polyester resin composition according to any one of claims 1 to 7, wherein the (b) olefin resin has an average particle diameter of 1 to 0.01 µm.

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