JP2005023093A - 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 100 pts. wt. of a resin composition composed of 60-95 wt.% of a polyester resin and 5-40 wt.% of an olefinic resin composed of an olefin copolymer prepared by introducing a monomer component having at least one kind of functional group selected from a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a metal carboxylate group and an epoxy group into an olefinic polymer and an ethylene/α-olefinic copolymer obtained by copolymerizing ethylene with a 3-20C α-olefin and 0.5-30 pts. wt. of a polyphenylene sulfide resin. The polyester resin composition has morphology in which the polyester resin forms a continuous phase and the olefinic resin is dispersed with 0.01-2 μm average particle diameter in the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００４８】
（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。 エチレンおよび／または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／メタクリル酸グリシジル共重合体、エチレン／ブテン−１／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。
【００４９】
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を有する一種以上の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。
【００５０】
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。
【００５１】
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。
【００５２】
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６０〜９５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７０〜８５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およ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。
【００５３】
さらに、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６０〜９５重量％であり、好ましくは（ｂ−１）成分が１０〜３０重量％、（ｂ−２）成分が７０〜９０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。
【００５４】
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重要である。
【００５５】
本発明に用いる（ｃ）ＰＰＳとしては、下記構造式で示される繰り返し単位を有する重合体を用いることができ、
【００５６】
【化２】

【００５７】
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、さらには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。
【００５８】
【化３】

【００５９】
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ように得られた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できる。
【００６０】
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ことができる。
【００６１】
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。
【００６２】
本発明で用いられる（ｃ）ＰＰＳは洗浄処理を施されたＰＰＳであることが好ましい。かかる洗浄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。
【００６３】
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。
【００６４】
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、常圧である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。
【００６５】
また、熱水で洗浄処理するする場合、周期表の第ＩＩ族の金属元素を含有する水溶液で処理することが好ましく用いられる。周期表の第ＩＩ族の金属元素を含む水溶液とは、上記水に、周期表の第ＩＩ族の金属元素を有する水溶性塩を添加したものである。水に対する周期表の第ＩＩ族の金属元素を有する水溶性塩の濃度は、０．００１〜５重量％程度の範囲が好ましい。
【００６６】
ここで使用する周期表の第ＩＩ族の金属元素の中でも好ましい金属元素としては、Ｃａ、Ｍｇ、ＢａおよびＺｎなどが例示でき、その対アニオンとしては、酢酸イオン、ハロゲン化物イオン、水酸化物イオンおよび炭酸イオンなどが挙げられる。より具体的で好適な化合物としては、酢酸Ｃａ、酢酸Ｍｇ、酢酸Ｚｎ、ＣａＣｌ _２ 、ＣａＢｒ_２ 、ＺｎＣｌ_２ 、ＣａＣＯ_３ 、Ｃａ（ＯＨ）_２ およびＣａＯなどが例示でき、特に好ましくは、酢酸Ｃａである。
【００６７】
周期表の第ＩＩ族の金属元素を含有する水溶液の温度は１３０℃以上であり、１５０℃以上がより好ましい。洗浄温度の上限については特に制限はないが、通常のオートクレーブを用いる場合には２５０℃程度が限界である。
【００６８】
かかる周期表の第ＩＩ族の金属元素を含む水溶液の浴比は、重量比で乾燥ポリマー１に対し、２〜１００の範囲が好ましく選択され、４〜５０の範囲がより好ましく、５〜１５の範囲であることがさらにに好ましい。
【００６９】
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。
【００７０】
本発明で用いられる（ｃ）ＰＰＳの灰分量は、加工時の流動性や成形サイクルなどの特性を付与する点から０．１〜２重量％と比較的多い範囲が好ましく選択され、０．２〜１重量％の範囲がより好ましく、０．３〜０．８重量％の範囲であることが更に好ましい。
【００７１】
ここで、灰分量とは以下の方法により求めたＰＰＳ中の無機成分量を指す。
【００７２】
（１）５８３℃で焼成、冷却した白金皿にＰＰＳ５〜６ｇを秤量する。
【００７３】
（２）白金皿とともにＰＰＳを４５０〜５００℃で予備焼成する。
【００７４】
（３）５８３℃にセットしたマッフル炉に白金皿とともに予備焼成したＰＰＳ試料を入れ、完全に灰化するまで約６時間焼成する。
【００７５】
（４）デシケーター内で冷却後、秤量する。
【００７６】
（５）式：灰分量（重量％）＝（灰分の重量（ｇ）／試料重量（ｇ））×１００により灰分量を算出する。
【００７７】
本発明で用いられる（ｃ）ＰＰＳの溶融粘度は、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１〜２０００Ｐａ・ｓ（３００℃、剪断速度１０００ｓｅｃ^−１）の範囲が好ましく選択され、１〜２００Ｐａ・ｓの範囲がより好ましく、１〜５０Ｐａ・ｓの範囲であることがさらにに好ましい。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。
【００７８】
本発明で用いられる（ｃ）ＰＰＳの有機系低重合成分（オリゴマー）量の指標となるクロロホルム抽出量（ポリマー１０ｇ／クロロホルム２００ｍＬ、ソックスレー抽出５時間処理時の残差量から算出）は、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１〜５重量％と比較的多い範囲が好ましく選択され、１．５〜４重量％の範囲がより好ましく、２〜４重量％の範囲であることがさらにに好ましい。
【００７９】
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、耐加水分解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０．５〜３０重量部であり、より好ましくは１〜２０重量部、特に好ましくは３〜１５重量部である。
【００８０】
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。
【００８１】
さらに本発明においては、高い耐熱性およ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。
【００８２】
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。
【００８３】
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。
【００８４】
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。
【００８５】
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。
【００８６】
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。ただし、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。
【００８７】
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。上記化合物はいずれも組成物全体の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、さらに好ましくは１重量％以下の添加がよい。
【００８８】
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。
【００８９】
本発明のポリエステル樹脂組成物は、低温での柔軟性およ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が分散相を形成する（海−島構造）ことが重要であり、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０．０１〜２μｍ、好ましくは０．０１〜１μｍで分散し、ポリエステル樹脂が連続相をなすモルホロジーとなることが低温特性、耐薬品性および流動性の点から重要である。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上、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。
【００９０】
ここでいう平均粒子径とは、ＰＰＳの融点＋０〜２０℃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。
【００９１】
本発明のポリエステル樹脂組成物は、（ａ）ポリエステル樹脂のカルボキシル末端基量を３０〜８０ｅｑ／ｔの範囲を選択し、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が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が５００〜２０００Ｊ／ｍであることが好ましく、さらに好ましくは引張り破断伸度が３０〜４００％、ノッチ付きアイゾット衝撃強度が６００〜２０００Ｊ／ｍであり、２３℃のヘキサフルオロイソプロパノール（以下ＨＦＩＰと略す）に１時間浸漬後の重量減少率が０〜５％、さらには６０℃、９５％ＲＨ、３０００時間処理後のＡＳＴＭ−Ｄ６３８に従って測定したポリエステル樹脂組成物を成形してなる成形品の引張り破断伸度が３０〜２００％であることが好ましい。
【００９２】
本発明のポリエステル樹脂組成物は、射出成形時の成形加工性、成形サイクルを向上させるために（ａ）ポリエステル樹脂にポリエチレンテレフタレートを用いた場合、生成樹脂組成物の示差熱量測定において、３００℃から２０℃／分の降温条件で測定した際に観測される発熱ピーク温度（Ｔｍｃ）が１９０〜２２０℃であることが好ましく、さらに好ましくは１９５〜２２０℃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重要であり、また、混練時の滞留時間を短くすることである。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ＰＰＳの融点＋０〜２０℃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、ケースなどの構造体、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さら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系樹脂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。ただし、ポリブチレンテレフタレート樹脂系は、シリンダー温度２６０℃、金型温度８０℃で行った。
【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（１／８インチ厚み）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（１／８インチ厚み）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。
二重丸：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】
［耐ＨＦＩＰ性］
ＡＳＴＭ１号ダンベル片を２３℃×１時間ヘキサフルオロイソプロパノール（ＨＦＩＰ）浸漬処理後の重量を秤量し計算した。
重量減少率＝［（処理前重量−浸漬処理後重量）÷処理前重量］×１００［％］
［耐加水分解性］
ＡＳＴＭ１号ダンベル片を６０℃、９５％ＲＨの恒温高湿条件下で３０００時間処理後の引張破断伸度をＡＳＴＭ−Ｄ６３８に従って測定した。
【０１０４】
［灰分量］
（１）５８３℃で焼成、冷却した白金皿にＰＰＳ５〜６ｇを秤量する。
【０１０５】
（２）白金皿とともにＰＰＳを４５０〜５００℃で予備焼成する。
【０１０６】
（３）５８３℃にセットしたマッフル炉に白金皿とともに予備焼成したＰＰＳ試料を入れ、完全に灰化するまで約６時間焼成する。
【０１０７】
（４）デシケーター内で冷却後、秤量する。
【０１０８】
（５）式：灰分量（重量％）＝（灰分の重量（ｇ）／試料重量（ｇ））×１００により灰分量を算出する。
【０１０９】
［クロロホルム抽出量］
ＰＰＳポリマー１０ｇを円筒形濾紙に秤量し、クロロホルム２００ｍＬでソックスレー抽出（バス温１２０℃、５時間）を行った。抽出後クロロホルムを除去し、残差量を秤量しポリマー重量当たりで計算した。
【０１１０】
［発熱ピーク温度（Ｔｍｃ）］
パーキンエルマー社製ＤＳＣ−７を用い、サンプルポリマー量約８ｍｇ、３００℃で５分間ホールドの後、降温速度２０℃／分の条件でスキャンすることにより、発熱ピーク温度（Ｔｍｃ）を測定した。
【０１１１】
［成形サイクル］
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℃、ＡＳＴＭ１号ダンベル片２ヶ取り金型）によりＡＳＴＭ１号ダンベル片を調製する際の良品成形品が得られる時間当たりの最高射出回数（ショット／ｈｒ）。ただし、ポリブチレンテレフタレート樹脂系は、シリンダー温度２６０℃、金型温度８０℃で行った。
【０１１２】
［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。
【０１１３】
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。
【０１１４】
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。
【０１１５】
得られたケークおよびイオン交換水１１８８０ｇ、酢酸カルシウム１水和物（シグマアルドリッチ）４ｇ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。
【０１１６】
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、灰分量０．６重量％、溶融粘度１２Ｐａ・ｓ（オリフィス０．５φ×１０ｍｍ、３００℃、剪断速度１０００ｓｅｃ^−１）、クロロホルム抽出量が３．８％であった。
【０１１７】
［参考例２］
ポリフェニレンスルフィド樹脂（Ｃ−２）の作製方法
撹拌機付きの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８４８ｇ（２０．４モル）、Ｎ−メチル−２−ピロリドン（ＮＭＰ）３２６７ｇ（３３モル）、酢酸ナトリウム５３１ｇ（６．５モル）、及びイオン交換水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を留出したのち、反応容器を１６０℃に冷却した。硫化水素の飛散量は、仕込みアルカリ金属硫化物１モル当たり０．０１８モルであった。
【０１１８】
次に、ｐ−ジクロロベンゼン（シグマアルドリッチ）３０３１ｇ（２０．６モル）、ＮＭＰ２５９４ｇ（２６．２モル）を加え、反応容器を窒素ガス下に密封し、４００ｒｐｍで撹拌しながら、２２７℃まで０．８℃／分の速度で昇温し、その後２７０℃まで０．６℃／分の速度で昇温し２７０℃で１４０分保持した。
その後２５０℃まで１．３℃／分の速度で冷却しながら６８４ｇ（３８モル）のイオン交換水をオートクレーブに圧入した。その後２００℃まで０．４℃／分の速度で冷却した後、室温近傍まで急冷した。
【０１１９】
内容物を取り出し、１０リットルのＮＭＰで希釈後、溶剤と固形物をふるい（８０ｍｅｓｈ）で濾別し、得られた粒子を２０リットルの温水で数回洗浄、濾別した。次いで１００℃に加熱されたＮＭＰ１０リットル中に投入して、約１時間攪拌し続けたのち、濾過し、さらに熱湯で数回洗浄した。次に９．８ｇの酢酸を含む２０リットルの温水で洗浄、濾別した後、２０リットルの温水で洗浄、濾別してＰＰＳポリマー粒子を得た。これを、８０℃で熱風乾燥し、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、灰分量０．０２重量％、溶融粘度４０Ｐａ・ｓ（オリフィス０．５φ×１０ｍｍ、３００℃、剪断速度１０００ｓｅｃ^−１）、クロロホルム抽出量が０．４％であった。
【０１２０】
［実施例１〜１３］、［比較例１〜６］
上記参考例記載の（Ｃ−１、Ｃ−２）ＰＰＳ成分および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℃、ただし、ポリブチレンテレフタレート樹脂系は、シリンダー温度２６０℃、金型温度８０℃）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、成形性、耐薬品性等に優れるのに対し、比較例においては低温特性、流動性、成形性、耐薬品性に劣るものであった。
【０１２１】
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０．６５、カルボキシル末端基量４５ｅｑ／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。
（Ａ−６）：固有粘度０．７５、カルボキシル末端基量３５ｅｑ／ｔ、融点２３４℃のポリエチレンテレフタレート／２，６−ナフタレンジカルボキシレート＝９２／８（モル％）樹脂。
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。
（Ｂ−３）： 無水マレイン酸変性のエチレン／プロピレン＝８５／１５モル％共重合体。
【０１２２】
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−４）： 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−５）： 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−６）： 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。
酸化防止剤：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。
【０１２３】
【表１】

【０１２４】
【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６９び耐衝撃性を有し、かつ流動性、成形加工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−島構造の一例を示すモデル図である。
【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一例を示すモデル図である。
【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 under 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, although molded articles obtained by these methods show good impact resistance near room temperature, for example, there is a problem that impact resistance is significantly lowered in a low temperature atmosphere of about −40 ° C., for example.
[0004]
On the other hand, conventionally, a method of blending a specific glycidyl group-containing olefin copolymer and an ethylene / α-olefin copolymer (see, for example, Patent Documents 1 and 2), an ethylene / vinyl acetate system in a specific polyester resin Improve impact resistance at low temperature by blending copolymer (for example, see Patent Document 3), blending impact-resistant component having acid anhydride group and specific glycidyl group-containing olefin copolymer Means (for example, see Patent Document 4) have been proposed.
[0005]
[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)
[0006]
[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.
[0007]
An object of the present invention is to provide a polyester resin composition having flexibility and impact resistance in a low temperature atmosphere superior to conventional materials, and excellent in fluidity, molding processability and chemical resistance. It is what.
[0008]
[Means for Solving the Problems]
Thus, as a result of studying the above problems, the present inventors have formed a specific morphology in a composition comprising (a) a polyester resin, (b) a specific olefin resin, and (c) a polyphenylene sulfide resin. As a result, the inventors have found that the above-mentioned problems have been solved, and that further remarkable effects can be obtained in chemical resistance, fluidity, molding processability, etc., and the present invention has been achieved.
[0009]
That is, the present invention adopts the following configuration in order to solve the above problems. That is,
(1) (a) 60 to 95% by weight of a polyester resin, and (b-1) an olefin polymer having a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal base, and an epoxy group. Ethylene / obtained by copolymerizing an olefin copolymer obtained by introducing a monomer component having at least one selected functional group, (b-2) ethylene, and an α-olefin having 3 to 20 carbon atoms. Containing 0.5 to 30 parts by weight of (c) polyphenylene sulfide resin with respect to 100 parts by weight of a resin composition comprising 5 to 40% by weight of (b) olefinic resin comprising α-olefin copolymer The resin composition has a morphology in which (a) the polyester resin forms a continuous phase and (b) the olefin resin is dispersed in the composition with an average particle size of 0.01 to 2 μm. Polyester resin composition characterized.
[0010]
(2) In the above (1), the (b-1) olefin copolymer is an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefin polymer. The polyester resin composition as described.
[0011]
(3) In the above (2), the (b-1) olefin copolymer is a copolymer of ethylene and / or an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester. The polyester resin composition as described.
[0012]
(4) The (a) polyester resin is at least one selected from polyethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate and copolymers thereof (1) to (1) The polyester resin composition according to any one of 3).
[0013]
(5) The polyester resin composition as described in any one of (1) to (4) above, wherein the ash content of the (c) polyphenylene sulfide resin is 0.1 to 2% by weight.
[0014]
(6) The (c) polyphenylene sulfide resin has a melt viscosity of 1 to 200 Pa · s (300 ° C., shear rate of 1000 sec ⁻¹ ), and a chloroform extraction amount of 1 to 5 wt%. The polyester resin composition according to any one of (1) to (5).
[0015]
(7) Tensile rupture of a molded product obtained by molding a polyester resin composition measured according to ASTM-D638 at a temperature of -40 ° C., wherein the amount of carboxyl end groups of the polyester resin is 30 to 80 eq / t. The polyester resin composition according to any one of (1) to (6) above, wherein the elongation is 20 to 400% and the Izod impact strength measured according to ASTM-D256 is 500 to 2000 J / m. .
[0016]
(8) Tensile rupture of a molded product obtained by molding a polyester resin composition measured according to ASTM-D638 at a temperature of -40 ° C., wherein the amount of carboxyl end groups of the polyester resin is 40 to 70 eq / t. The polyester resin composition as described in (7) above, having an elongation of 30 to 400% and an Izod impact strength of 600 to 2000 J / m as measured according to ASTM-D256.
[0017]
(9) The amount of carboxyl end groups of the (a) polyester resin is 30 to 80 eq / t, and the weight reduction rate after being immersed in hexafluoroisopropanol at 23 ° C. for 1 hour is 0 to 5%. The polyester resin composition according to any one of (1) to (6).
[0018]
(10) The polyester resin composition (a) having a carboxyl terminal group amount of 30 to 80 eq / t and molding a polyester resin composition measured in accordance with ASTM-D638 after treatment at 60 ° C., 95% RH for 3000 hours. The polyester resin composition according to any one of (1) to (6) above, wherein the molded article has a tensile elongation at break of 30 to 200%.
[0019]
(11) The exothermic peak temperature (Tmc) observed when the polyester resin (a) is polyethylene terephthalate and is measured under a temperature drop condition from 300 ° C. to 20 ° C./min in the differential calorimetry of the resulting resin composition. The polyester resin composition according to any one of the above (1) to (10), wherein the temperature is 190 ° C. or higher.
[0020]
(12) The polyester resin composition according to any one of (1) to (11), wherein the average particle size of the (b) olefin resin is dispersed in a range of 0.01 to 1 μm. .
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail based on embodiments.
[0022]
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 a copolymer obtained by a condensation reaction mainly containing a hydroxycarboxylic acid.
[0023]
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′- Examples thereof include diphenyldicarboxylic 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
[0024]
Examples of the diol include aliphatic diols 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. , Cyclohexanedimethanol, cyclohexanediol, and the like, and ester-forming derivatives thereof. Two or more of these diols can be used in combination.
[0025]
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-naphthalene dicarboxylate, Polybutylene-2,6-naphthalene dicarboxylate, polyethylene-1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polybutylene terephthalate / Decane dicarboxylate, polyethylene terephthalate / 2,6-naphthalenedicarboxylate, poly (ethylene And non-liquid crystalline polyesters such as polyethylene-4,4′-dicarboxylate / terephthalate and mixtures thereof.
[0026]
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.
[0027]
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 performing an esterification reaction with a dicarboxylic acid and a diol as main components and then performing a polycondensation reaction under reduced pressure. The transesterification method is a method for producing a polyester resin by conducting an ester exchange reaction with an ester-forming derivative of a dicarboxylic acid and a diol as main components and then performing a polycondensation reaction under reduced pressure.
[0028]
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.
[0029]
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.
[0030]
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.
[0031]
In order to obtain a polyester resin having a relatively large amount of carboxyl end groups of 30 to 80 eq / t (the amount of end groups per ton of polymer) preferably used in the present invention, the polycondensation reaction time is set longer than before. It is preferable to do.
[0032]
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 preferable from the viewpoint of low temperature impact resistance. More 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 tends to deteriorate and the low-temperature characteristics tend to decrease, and if it exceeds 80 eq / t, hydrolysis tends to increase.
[0033]
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. It is in the range of 50 to 1.50, particularly preferably in the range of 0.50 to 1.20.
[0034]
Next, the (b) olefin resin used in the present invention is a combination of (b-1) a functional group-containing olefin copolymer and (b-2) an ethylene / α-olefin copolymer.
[0035]
Here, (b-1) an olefin copolymer having at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal base, and an epoxy group used in the present invention. Contains at least one of the functional groups in the molecule. Here, the olefin copolymer having a functional group is a monomer component having at least one functional group selected from a carboxylic acid group, a carboxylic anhydride group, a carboxylic acid ester group, a carboxylic acid metal base, and an epoxy group. It can obtain by introduce | transducing into an olefin copolymer.
[0036]
The monomer component having a functional group for introducing a functional group into the olefin polymer is a compound containing a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, and an epoxy group, for example, Acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2-ene-5,6- Examples thereof include unsaturated carboxylic acids such as dicarboxylic acids, or carboxylic acid anhydrides or carboxylic acid esters thereof. Specific examples of the compound include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride, maleic Dimethyl acid, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, dimethyl bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylate, Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, propyl methacrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, aminoethyl methacrylate and amino Propyl and the like.
[0037]
The method for introducing the monomer component having a functional group is not particularly limited, and a method for copolymerizing the monomer component having the functional group with at least one olefin selected from ethylene and α-olefin, an olefin polymer. For example, a method of grafting can be used.
[0038]
Specific examples of at least one olefin selected from ethylene and α-olefin used for copolymerization include propylene, 1-butene, 2-butene, 1-pentene, and 3-methyl-1 in addition to ethylene. -Butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4 , 4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, -Olefins such as eicosene. Among these, one or more olefins selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable.
[0039]
Specific examples of the olefin polymer to be grafted onto the olefin polymer include high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, ethylene / propylene copolymer, and ethylene / butene-1 copolymer. Polymer, ethylene / hexene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, unhydrogenated or hydrogenated styrene / isoprene / styrene triblock Mention may be made of copolymers, unhydrogenated or hydrogenated styrene / butadiene / styrene triblock copolymers.
[0040]
In addition, when the monomer component having a functional group is graft-introduced to the olefin polymer, it is preferable to perform the grafting in the presence of a radical initiator because the graft reaction efficiency is increased. Examples of the radical initiator used here include organic peroxides and azo compounds. Specifically, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1 , 1-bis (t-butylperoxy) valerate, benzoyl peroxide, t-butylperoxybenzoate, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5 , 5-Trimethylhexanoyl peroxide and 2,4-dichlorobenzo , And the like peroxide and m- toluyl peroxide. Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile.
[0041]
The reaction conditions for the graft reaction as described above are not particularly limited, but it is preferably carried out in a state where the olefin polymer is melted. In this case, the reaction is usually carried out at a temperature equal to or higher than the melting point of the olefin polymer. That is, the graft polymerization reaction is carried out at a temperature equal to or higher than the melting point of the olefin copolymer, specifically in the range of usually 80 to 300 ° C, preferably 80 to 260 ° C.
[0042]
The polyolefin copolymer having a carboxylic acid metal base is obtained by metallizing a part or all of the carboxylic acid introduced as described above. Although there is no restriction | limiting in particular about the metal seed | species in a carboxylic acid metal base, Al, Sn, Sb, Ti, Mn, other than alkali metals, alkaline earth metals, such as Li, Na, K, Mg, Ca, Sr, Ba, etc. Fe, Ni, Cu, Zn, Cd and the like are used, and Zn is particularly preferably used.
[0043]
The introduction amount of the monomer component containing the functional group is 0.001 to 40 mol%, preferably 0.01 to 35 mol%, based on the total amount of the olefin copolymer containing the functional group (b-1). It is appropriate to be within the range.
[0044]
The olefin copolymer containing an epoxy group in the present invention is an olefin copolymer having at least one epoxy group in the molecule. Preferably, it is an olefin copolymer containing ethylene and / or an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid as a copolymerization component. 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.
[0045]
In the present invention, it is particularly preferable to use an olefin copolymer comprising ethylene and a glycidyl ester of an α, β-unsaturated carboxylic acid as a component. An olefin copolymer having 1 to 40% by weight of a glycidyl ester as a copolymerization component is particularly preferable.
[0046]
As the glycidyl ester of the α, β-unsaturated carboxylic acid,
[0047]
[Chemical 1]

[0048]
(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. Specific examples of the olefin copolymer containing ethylene and / or α-olefin and glycidyl ester of α, β-unsaturated carboxylic acid as essential copolymerization components include ethylene / propylene / glycidyl methacrylate copolymer, ethylene / Butene-1 / glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / methacrylic acid A glycidyl copolymer is mentioned. Of these, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, and ethylene / methyl methacrylate / glycidyl methacrylate copolymer are preferably used.
[0049]
Further, (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 one or more α having ethylene and 3 to 20 carbon atoms. -A copolymer containing olefin as a constituent. 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.
[0050]
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.
[0051]
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.
[0052]
The blending ratio of (a) polyester resin and (b) olefin resin of the present invention is 60 to 95% by weight of polyester resin and 5 to 40% by weight of olefin resin, preferably 70 to 85% 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 improve the flexibility and impact resistance. On the other hand, if it exceeds 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.
[0053]
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), 60 to 95% by weight of component (b-2), preferably 10 to 30% by weight of component (b-1), based on the total of both. , (B-2) component is 70 to 90% 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.
[0054]
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 important to contain.
[0055]
As (c) PPS used in the present invention, a polymer having a repeating unit represented by the following structural formula can be used.
[0056]
[Chemical 2]

[0057]
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.
[0058]
[Chemical 3]

[0059]
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, acid aqueous solution, etc., activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates, functional group-containing disulfide compounds Can be used on that has been subjected.
[0060]
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 drier or a heating apparatus with a rotary or stirring blade, but a heating apparatus with a rotary or stirring blade should be used for efficient and more uniform treatment. Can do.
[0061]
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.
[0062]
The (c) PPS used in the present invention is preferably PPS that has been subjected to a cleaning treatment. Specific examples of the washing treatment include an acid aqueous solution washing treatment, a hot water washing treatment, and an organic solvent washing treatment, and these treatments may be used in combination of two or more methods.
[0063]
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.
[0064]
The following method can be illustrated as a specific method when the PPS is washed with hot water. That is, it is preferable that the water used is distilled water or deionized water in order to exhibit the effect of preferable chemical modification of PPS by hot water washing. The operation of the hot water treatment is usually carried out 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.
[0065]
Moreover, when wash-processing with hot water, it is preferable to use the aqueous solution containing the Group II metal element of the periodic table. The aqueous solution containing a Group II metal element of the periodic table is obtained by adding a water-soluble salt containing a Group II metal element of the periodic table to the water. The concentration of the water-soluble salt having a Group II metal element in the periodic table with respect to water is preferably in the range of about 0.001 to 5% by weight.
[0066]
Examples of preferable metal elements among Group II metal elements of the periodic table used herein include Ca, Mg, Ba and Zn, and the counter anions thereof include acetate ions, halide ions, hydroxide ions. And carbonate ions. More specific and preferred compounds include Ca acetate, Mg acetate, Zn acetate, CaCl ₂ , CaBr ₂ , ZnCl ₂ , CaCO ₃ , Ca (OH) ₂ and CaO, and particularly preferably Ca acetate. is there.
[0067]
The temperature of the aqueous solution containing the Group II metal element of the periodic table is 130 ° C. or higher, and more preferably 150 ° C. or higher. Although there is no restriction | limiting in particular about the upper limit of washing | cleaning temperature, When using a normal autoclave, about 250 degreeC is a limit.
[0068]
The bath ratio of the aqueous solution containing the Group II metal element of the periodic table is preferably selected in the range of 2 to 100, more preferably 4 to 50, and 5 to 15 with respect to the dry polymer 1 by weight ratio. More preferably, it is in the range.
[0069]
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.
[0070]
The amount of ash content of (c) PPS used in the present invention is preferably selected in a relatively large range of 0.1 to 2% by weight from the viewpoint of imparting characteristics such as fluidity at the time of processing and molding cycle. The range of ˜1% by weight is more preferred, and the range of 0.3˜0.8% by weight is still more preferred.
[0071]
Here, the amount of ash refers to the amount of inorganic components in PPS determined by the following method.
[0072]
(1) Weigh 5-6 g of PPS in a platinum dish fired and cooled at 583 ° C.
[0073]
(2) PPS is pre-fired at 450 to 500 ° C. together with a platinum dish.
[0074]
(3) Put a PPS sample pre-fired with a platinum pan in a muffle furnace set at 583 ° C., and fire it for about 6 hours until it completely incinerates.
[0075]
(4) Weigh after cooling in a desiccator.
[0076]
(5) Calculate the ash content by the formula: ash content (% by weight) = (weight of ash content (g) / sample weight (g)) × 100.
[0077]
The melt viscosity of (c) PPS used in the present invention is in the range of ¹ to 2000 Pa · s (300 ° C., shear rate 1000 sec ⁻¹ ) in terms of imparting properties such as improved chemical resistance and fluidity during processing. Is preferably selected, more preferably in the range of 1 to 200 Pa · s, and still more preferably in the range of 1 to 50 Pa · s. Here, the melt viscosity is a value measured by a Koka flow tester using a nozzle having a nozzle diameter of 0.5 mmφ and a nozzle length of 10 mm under the condition of a shear rate of 1000 sec ⁻¹ .
[0078]
(C) Chloroform extraction amount (calculated from the residual amount at the time of 5-hour treatment with Soxhlet extraction), which is an index of the amount of the organic low polymerization component (oligomer) of PPS used in the present invention, is a chemical resistance From the point of imparting characteristics such as improvement of properties and fluidity during processing, a relatively large range of 1 to 5% by weight is preferably selected, a range of 1.5 to 4% by weight is more preferred, and 2 to 4% by weight More preferably, it is the range.
[0079]
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, From the point which provides characteristics, such as improvement of hydrolysis resistance and the fluidity | liquidity at the time of processing, it is 0.5-30 weight part with respect to the total 100 weight part of (a) and (b), More preferably, it is 1 20 parts by weight, particularly preferably 3 to 15 parts by weight.
[0080]
The polyester resin composition of the present invention can further contain an antioxidant or other additives as described below.
[0081]
Further, 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.
[0082]
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.
[0083]
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.
[0084]
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.
[0085]
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.
[0086]
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, if this amount exceeds 30% by weight of the whole composition, the original characteristics of the polyester resin are impaired, and the addition of 20% by weight or less is particularly preferred.
[0087]
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, the addition is preferably not more than 10% by weight, more preferably not more than 1% by weight.
[0088]
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.
[0089]
In the polyester resin composition of the present invention, the polyester resin 1 forms a continuous phase (matrix) as shown in FIG. Is important to form a dispersed phase (sea-island structure), and the average particle diameter of the olefin resin forming the dispersed phase is 0.01 to 2 μm, preferably 0.01 to 1 μm, It is important from the viewpoint of low-temperature characteristics, chemical resistance, and fluidity that the polyester resin has a morphology that forms a continuous phase. Here, the morphology of the present invention is not limited to the form of FIG. 1, and the shape of the olefin resin particles may be non-circular in shape such as polygonal or substantially elliptical. 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.
[0090]
The average particle diameter here means that the ASTM No. 1 dumbbell piece is molded at a molding temperature of PPS melting point + 0 to 20 ° C., and a thin piece of 0.1 μm or less (about 80 nm) from the center is formed in the cross-sectional area direction of the dumbbell piece. Cutting and observing with a transmission electron microscope (magnification: 10,000 times), the dispersed portions of 100 arbitrary olefin-based resins are first measured for their maximum and minimum diameters, and then averaged. It is the number average particle diameter for which the average value was obtained.
[0091]
In the polyester resin composition of the present invention, (a) the carboxyl terminal group amount of the polyester resin is selected in the range of 30 to 80 eq / t, and the above morphology is formed, so that the temperature is -40 ° C under ASTM-D638. It is preferable that the tensile elongation at break measured according to ASTM-D is 20 to 400%, and the Izod impact strength with notch measured according to ASTM-D256 is 500 to 2000 J / m, more preferably the tensile elongation at break is 30 to 400%. The notched Izod impact strength is 600 to 2000 J / m, and the weight loss after immersion in hexafluoroisopropanol (hereinafter abbreviated as HFIP) at 23 ° C. for 1 hour is 0 to 5%, and further 60 ° C. and 95% RH. A polyester resin composition measured according to ASTM-D638 after 3000 hours of treatment was formed. It is preferable tensile elongation at break of a molded article was formed by is 30 to 200%.
[0092]
When the polyester resin composition of the present invention uses polyethylene terephthalate as the polyester resin in order to improve the molding processability and molding cycle at the time of injection molding, in the differential calorimetry of the resulting resin composition, from 300 ° C. It is preferable that the exothermic peak temperature (Tmc) observed when measured under a temperature drop condition of 20 ° C./min is 190 to 220 ° C., more preferably 195 to 220 ° C.
[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. A typical example is a method of kneading at the processing temperature, but in order to control the morphology of the present invention and the particle size of the olefin copolymer as described above, it is important to make the shearing force relatively strong. Moreover, it is to shorten the residence time at the time of 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 PPS + 0 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 electrical 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]
The m-cresol solution was determined by potentiometric titration 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 part with a transmission electron microscope. Observed 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 size]
The average particle diameter of the olefin resin is measured by using image processing software “Scion Image” for a dispersion portion of 100 arbitrary olefin resins in the injection molded product observed at a magnification of 10,000 as in the above morphological observation. Then, the maximum diameter and the minimum diameter of each particle were measured to obtain an average value, and then the number average value thereof was obtained.
[0099]
[Lower molding pressure]
The minimum filling pressure when preparing a test piece by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C.) was determined. However, the polybutylene terephthalate resin system was performed at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C.
[0100]
[-40 ° C Izod impact strength]
The notched Izod impact strength (1/8 inch thickness) was measured according to ASTM-D256 except that the temperature atmosphere was -40 ° C.
[0101]
[−40 ° C. tensile elongation at break]
The tensile elongation at break (1/8 inch thickness) was measured according to ASTM-D638 except that the temperature atmosphere was set to -40 ° C.
[0102]
[chemical resistance]
The surface of the 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.
Double circle: 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]
[HFIP resistance]
ASTM 1 dumbbell pieces were weighed and calculated after immersion in hexafluoroisopropanol (HFIP) at 23 ° C. for 1 hour.
Weight reduction rate = [(weight before treatment−weight after immersion treatment) ÷ weight before treatment] × 100 [%]
[Hydrolysis resistance]
The tensile elongation at break after 3000 hour treatment of ASTM No. 1 dumbbell pieces under constant temperature and high humidity conditions of 60 ° C. and 95% RH was measured according to ASTM-D638.
[0104]
[Ash content]
(1) Weigh 5-6 g of PPS in a platinum dish fired and cooled at 583 ° C.
[0105]
(2) PPS is pre-fired at 450 to 500 ° C. together with a platinum dish.
[0106]
(3) Put a PPS sample pre-fired with a platinum pan in a muffle furnace set at 583 ° C., and fire it for about 6 hours until it completely incinerates.
[0107]
(4) Weigh after cooling in a desiccator.
[0108]
(5) Calculate the ash content by the formula: ash content (% by weight) = (weight of ash content (g) / sample weight (g)) × 100.
[0109]
[Chloroform extraction amount]
10 g of PPS polymer was weighed on a cylindrical filter paper, and Soxhlet extraction (bath temperature 120 ° C., 5 hours) was performed with 200 mL of chloroform. After extraction, chloroform was removed, and the residual amount was weighed and calculated per polymer weight.
[0110]
[Exothermic peak temperature (Tmc)]
Using DSC-7 manufactured by PerkinElmer, the exothermic peak temperature (Tmc) was measured by scanning at a temperature drop rate of 20 ° C./min after holding the sample polymer amount of about 8 mg and holding at 300 ° C. for 5 minutes.
[0111]
[Molding cycle]
Per time when good molded products are obtained when preparing ASTM No. 1 dumbbell pieces by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, Cylinder temperature 280 ° C., mold temperature 130 ° C., ASTM No. 1 dumbbell piece mold) Maximum number of injections (shot / hr). However, the polybutylene terephthalate resin system was performed at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C.
[0112]
[Reference Example 1]
Preparation Method of 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 of 96% sodium hydroxide ( 19.9 mol), 3960 g (40.0 mol) of N-methyl-2-pyrrolidone (NMP), and 3000 g of ion-exchanged water, and gradually heated to 225 ° C. over about 3 hours while passing nitrogen at normal pressure. 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.
[0113]
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.
[0114]
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.
[0115]
The obtained cake, 11880 g of ion-exchanged water, and 4 g of calcium acetate monohydrate (Sigma Aldrich) were charged into an autoclave equipped with a stirrer, and the inside of the autoclave was replaced with nitrogen, then the temperature was raised to 192 ° C. and held for 30 minutes. . Thereafter, the autoclave was cooled and the contents were taken out.
[0116]
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 had an ash content of 0.6% by weight, a melt viscosity of 12 Pa · s (orifice 0.5φ × 10 mm, 300 ° C., shear rate of 1000 sec ⁻¹ ), and a chloroform extraction amount of 3.8%.
[0117]
[Reference Example 2]
Preparation method of polyphenylene sulfide resin (C-2) In a 20 liter autoclave equipped with a stirrer, 2383 g (20.0 mol) of 47% sodium hydrosulfide (Sankyo Kasei), 848 g (20.4 mol) of 96% sodium hydroxide , 3267 g (33 mol) of N-methyl-2-pyrrolidone (NMP), 531 g (6.5 mol) of sodium acetate, and 3000 g of ion-exchanged water were gradually added to 225 ° C. over about 3 hours while passing nitrogen at normal pressure. And 4200 g of water and 80 g of NMP were distilled off, and then the reaction vessel was cooled to 160 ° C. The amount of hydrogen sulfide scattered was 0.018 mol per mol of the charged alkali metal sulfide.
[0118]
Next, 3031 g (20.6 mol) of p-dichlorobenzene (Sigma Aldrich) and 2594 g (26.2 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 400 rpm to reach 227 ° C. The temperature was raised at a rate of 8 ° C./min, then raised to 270 ° C. at a rate of 0.6 ° C./min and held at 270 ° C. for 140 minutes.
Thereafter, 684 g (38 mol) of ion-exchanged water was injected into the autoclave while cooling to 250 ° C. at a rate of 1.3 ° C./min. Then, after cooling to 200 ° C. at a rate of 0.4 ° C./min, it was rapidly cooled to near room temperature.
[0119]
The contents were taken out, diluted with 10 liters of NMP, the solvent and solids were filtered off with a sieve (80 mesh), and the resulting particles were washed several times with 20 liters of warm water and filtered off. Next, the solution was put into 10 liters of NMP heated to 100 ° C., and stirred for about 1 hour, filtered, and further washed several times with hot water. Next, it was washed with 20 liters of warm water containing 9.8 g of acetic acid and filtered, and then washed with 20 liters of warm water and filtered to obtain PPS polymer particles. This was dried in hot air at 80 ° C. and vacuum-dried at 120 ° C. for 24 hours to obtain dry PPS. The obtained PPS had an ash content of 0.02% by weight, a melt viscosity of 40 Pa · s (orifice 0.5φ × 10 mm, 300 ° C., shear rate of 1000 sec ⁻¹ ), and a chloroform extract amount of 0.4%.
[0120]
[Examples 1 to 13], [Comparative Examples 1 to 6]
After dry blending the (C-1, C-2) PPS components described in the above reference examples and the components shown below at the respective ratios shown in Table 1, the cylinders were manufactured using a TEX30 type twin screw extruder manufactured by Nippon Steel Works. The temperature was set to 250 to 280 ° C., melted and kneaded with a screw rotation of 200 rpm, and pelletized with a strand cutter. Using pellets dehumidified and dried at 120 ° C. overnight, injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C., but polybutylene terephthalate resin system has a cylinder temperature 260 ° C., mold A test piece was prepared at a temperature of 80 ° C. 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, moldability, chemical resistance, etc., the comparative example is inferior in low temperature characteristics, fluidity, moldability, and chemical resistance. It was a thing.
[0121]
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 0.65 and a carboxyl end group amount of 45 eq / t.
(A-6): Polyethylene terephthalate / 2,6-naphthalenedicarboxylate = 92/8 (mol%) resin having an intrinsic viscosity of 0.75, a carboxyl end group amount of 35 eq / t, and a melting point of 234 ° C.
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.
(B-3): Maleic anhydride modified ethylene / propylene = 85/15 mol% copolymer.
[0122]
Similarly, the (b-2) olefin resin is as follows.
(B-4): MFR = 3.5 g / 10 min (190 ° C., 2.16 kg load), ethylene / 1-butene copolymer having a density of 0.864 g / cm ³ .
(B-5): MFR = 0.5 g / 10 min (190 ° C., 2.16 kg load), ethylene / 1-butene copolymer having a density of 0.861 g / cm ³ .
(B-6): MFR = 0.4 g / 10 min (190 ° C., 2.16 kg load) ethylene / propylene = 85/15 mol% copolymer.
Antioxidant: The following two types of compounds were used.
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.
[0123]
[Table 1]

[0124]
【The invention's effect】
According to the present invention, the injection molding has excellent mechanical properties, particularly excellent flexibility 69 and impact resistance in a low temperature atmosphere of −40 ° C., and excellent fluidity, molding processability and chemical resistance. A suitable polyester resin composition is obtained.
[Brief description of the drawings]
FIG. 1 is a model diagram showing an example 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 showing an example 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 (12)

(A) 60 to 95% by weight of a polyester resin, and (b-1) at least selected from a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal base, and an epoxy group in the olefin polymer. Ethylene / α-olefin obtained by copolymerizing an olefin copolymer obtained by introducing a monomer component having one kind of functional group and (b-2) ethylene and an α-olefin having 3 to 20 carbon atoms (B) a resin composition containing 0.5 to 30 parts by weight of a polyphenylene sulfide resin with respect to 100 parts by weight of a resin composition comprising (b) 5 to 40% by weight of an olefin resin. Wherein (a) the polyester resin forms a continuous phase and (b) the olefinic resin has a morphology in which the average particle size is 0.01 to 2 μm dispersed in the composition. Polyester resin composition according to. The polyester resin according to claim 1, wherein the (b-1) olefin copolymer is an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefin polymer. Composition. The polyester resin according to claim 2, wherein the (b-1) olefin copolymer is a copolymer of ethylene and / or an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester. 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. The polyester resin composition according to any one of claims 1 to 4, wherein an ash content of the (c) polyphenylene sulfide resin is 0.1 to 2% by weight. The melt viscosity of the (c) polyphenylene sulfide resin is 1 to 200 Pa · s (300 ° C., shear rate 1000 sec ⁻¹ ), and the chloroform extraction amount is 1 to 5% by weight. The polyester resin composition according to any one of 5. (A) The amount of carboxyl end groups of the polyester resin is 30 to 80 eq / t, and the tensile elongation at break of the molded product obtained by molding the 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 is 20 to 400% and has an Izod impact strength of 500 to 2000 J / m measured according to ASTM-D256. (A) The amount of carboxyl end groups of the polyester resin is 40 to 70 eq / t, and 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. The polyester resin composition according to claim 7, which is 30 to 400% and has an Izod impact strength of 600 to 2000 J / m measured according to ASTM-D256. (A) The amount of carboxyl end groups of the polyester resin is 30 to 80 eq / t, and the weight reduction rate after being immersed in hexafluoroisopropanol at 23 ° C. for 1 hour is 0 to 5%. Item 7. The polyester resin composition according to any one of Items 1 to 6. Molding formed by molding a polyester resin composition having a carboxyl terminal group amount of (a) polyester resin of 30 to 80 eq / t and measured according to ASTM-D638 after treatment at 60 ° C. and 95% RH for 3000 hours. The polyester resin composition according to any one of claims 1 to 6, wherein the product has a tensile elongation at break of 30 to 200%. The (a) polyester resin is polyethylene terephthalate, and the exothermic peak temperature (Tmc) observed when measured under a temperature drop condition from 300 ° C. to 20 ° C./min in the differential calorimetry of the resulting resin composition is 190 ° C. It is the above, The polyester resin composition in any one of Claims 1-10 characterized by the above-mentioned. 12. The polyester resin composition according to claim 1, wherein the (b) olefin resin has an average particle diameter of 0.01 to 1 μm.

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