JP4770107B2 - Containers or accessories for transporting or storing chemicals and / or gases - Google Patents

Description

【００５１】
（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。
【００５２】
また、本発明では（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を用い、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。
【００５３】
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がある。
【００５４】
本発明に用いるオレフィン系樹脂（ｂ）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。
【００５５】
本発明のポリエステル樹脂（ａ）とオレフィン系樹脂（ｂ）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、耐透過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。
【００５６】
更に、本発明においては、上記の如く官能基含有オレフィン系共重合体（ｂ−１）とエチレン・α−オレフィン系共重合体（ｂ−２）を併用して用いる。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。
【００５７】
本発明の成形に用いる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。
【００５８】
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一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。
【００５９】
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。
【００６０】
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。
【００６１】
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。
【００６２】
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。
【００６３】
さらに、本発明に用い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本発明に用いる組成物全体の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。
【００６４】
本発明のポリエステル樹脂組成物を加工してなる薬液および／またはガスの搬送または貯蔵用の容器もしくはその付属部品は、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。
【００６５】
本発明の薬液および／またはガスの搬送または貯蔵用の容器もしくはその付属部品の製造に用いる樹脂組成物は、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であり、燃料（（トルエン／／イソオクタン＝５０／／５０体積％）とエタノールを９０対１０重量比に混合したアルコールガソリン混合物）の６０℃での透過係数が５０ｇ・ｍｍ／ｍ²・２４ｈｒ以下であることが好ましく、更に好ましくは、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、燃料（（トルエン／／イソオクタン＝５０／／５０体積％）とエタノールを９０対１０重量比に混合したアルコールガソリン混合物）の６０℃での透過係数が３０ｇ・ｍｍ／ｍ²・２４ｈｒ以下であることが好ましい。上記特性を有するポリエステル樹脂組成物を加工して薬液および／またはガスの搬送または貯蔵用の容器もしくはその付属部品とすることにより、例えば、自動車ガソリンタンクに用いる場合、車両追突時などの衝撃破壊性に優れると共に、ガソリンの耐透過性にも優れることから、非常に有用なガソリンタンクを得ることが可能となる。
【００６６】
本発明に用いるポリエステル樹脂組成物の製造は、単軸、２軸の押出機、バンバリーミキサー、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を用いて行われ、各々の成分を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。また、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、この樹脂組成物の製造時に溶融混練される樹脂に与えられる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が必要である。これらの条件を組み合わせることによって樹脂組成物中での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ため、その後の射出成形時においてもオレフィン系共重合体が凝集することを防ぐことができ、本発明のモルフォロジーとすることが可能になるからである。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＋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。
【００６７】
本発明の薬液および／またはガスの搬送または貯蔵用の容器もしくはその付属部品は、低温での柔軟性及び耐衝撃性の高度の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）ことが必要であり、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、耐透過性および流動性の点から必要である。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、耐透過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透過性が低下する。本発明のモルホロジーである場合には低温特性に優れ、耐透過性、流動性が特に優れる。
【００６８】
ここでいう平均粒子径とは、ポリエステル樹脂の融点＋２０℃の加工温度でモデル容器を射出成形し、その厚み方向の中心部から０．１μｍ以下（約８０ｎｍ）の薄片を切削し、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。
【００６９】
本発明の薬液および／またはガスの搬送または貯蔵用の容器もしくはその付属部品の加工方法に関しては、特に制限はなく、公知の方法（射出成形、押出成形、吹込成形、プレス成形等）を利用することができるが、生産上好ましい方法は、射出成形である。射出成形とは、可塑化装置で溶融されたポリエステル樹脂組成物を金型キャビティに加圧状態で注入し、金型内で固化させて成形品を得るもの全てを指し、通常の射出成形に加え例えば射出圧縮成形も含む。また、加工温度については、通常、ポリエステル樹脂の融点＋５〜融点＋５０℃高い温度範囲から選択される。また、成形法は一般的には、単層であるが、２色成形法により多層にしてもかまわない。
【００７０】
本発明のポリエステル樹脂組成物を加工してなる薬液および／またはガスの搬送または貯蔵用の容器もしくはその付属部品の好ましい成形方法は、容器もしくはその付属部品を構成する２つ以上の分割体を射出成形によって形成し、次いでこれらを相互に接合することによって形成する方法である。分割体同士を接合する方法は特に限定されず公知の方法（熱板溶着、振動溶着、射出溶着、超音波溶着、レーザー溶着、マイクロ波溶着）を用いることが可能である。
【００７１】
熱板溶着法の場合、分割体の接合面を熱板により溶融させ、素早く分割体の接合面どうしを圧接させて溶着させる。この際の熱板条件としては、通常の条件をとればよく、例えば接触法の場合、熱板温度２３０〜３５０℃、溶融時間２０〜６０秒を採用することができる。
【００７２】
振動溶着法の場合、分割体の接合面どうしを上下に圧接させた状態とし、この状態で横方向に振動を与えて発生する摩擦熱によって溶着させる。この際の振動条件としては通常の条件をとればよく、例えば、振動数１００〜３００Ｈｚ、振幅０．５〜２．０ｍｍを採用することができる。
【００７３】
熱線溶着法の場合、例えば鉄−クロム製の線材を分割体の接合部に埋め込んだ状態で接合面どうしを圧接し、線材に電流をかけジュール熱を発生させその発熱によって接合面を溶着させる。
【００７４】
射出溶着法の場合、分割体を金型内にインサートし、又は金型内で位置変更した後に、接合面を合わせた状態で保持し、その接合部の周縁に新たに溶融樹脂を射出して各分割体を互いに溶着させて中空容器を成形する。この際の射出溶着条件としては通常の条件をとればよく、例えば、樹脂温度２３０〜３２０℃、射出圧力１０〜１５０ＭＰａ、型締め力１００〜４０００トン、金型温度３０〜１５０℃を採用することができる（尚、前記記載の金型内で位置変更して行なう方法は、ダイスライド成形や、ダイ回転成形などともいわれている）。
【００７５】
レーザー溶着法の場合、レーザー光に対して非吸収性の分割体とレーザー光に対して吸収性の分割体を接合面で重ね合わせた状態で、非吸収性の分割体側からレーザー光を照射して溶着させる。また、レーザー光吸収性とするためには、カーボンブラックを本発明の製造に用いる樹脂組成物に添加する手法をあげることができる。カーボンブラックを添加することで照射されるレーザー光の透過率を５％以下とすることができ、レーザー光のエネルギーを効率的に熱に変換することが可能となる。この際のレーザー溶着条件としては通常の条件をとればよく、例えば、レーザー光として、ＹＡＧレーザー、レーザー光波長８００〜１０６０ｎｍ、レーザー光出力５〜３０Ｗを採用することができる。
【００７６】
本発明の薬液および／またはガスの搬送または貯蔵用の容器もしくはその付属部品は、例えば、フロン−１１、フロン−１２、フロン−２１、フロン−２２、フロン−１１３、フロン−１１４、フロン−１１５、フロン−１３４ａ、フロン−３２、フロン−１２３、フロン−１２４、フロン−１２５、フロン−１４３ａ、フロン−１４１ｂ、フロン−１４２ｂ、フロン−２２５、フロン−Ｃ３１８、Ｒ−５０２、１，１，１−トリクロロエタン、塩化メチル、塩化メチレン、塩化エチル、メチルクロロホルム、プロパン、イソブタン、ｎ−ブタン、ジメチルエーテル、ひまし油ベースのブレーキ液、グリコールエーテル系ブレーキ液、ホウ酸エステル系ブレーキ液、極寒地用ブレーキ液、シリコーン油系ブレーキ液、鉱油系ブレーキ液、パワースアリリングオイル、ウインドウオッシャ液、ロングライフクーラント液（ＬＬＣ液）、ガソリン、メタノール、エタノール、イソプタノール、ブタノール、窒素、酸素、水素、二酸化炭素、メタン、プロパン、天然ガス、アルゴン、ヘリウム、キセノン、医薬剤等の気体および／または液体あるいは気化ガス等の透過性が低く優れていることから、燃料タンク、オイル用タンク、ラジエタータンク、各種薬剤用ボトルなどの薬液保存容器用途に有効である。また、これらタンク、ボトルに付属するカットオフバルブなどのバルブや継手類、付属ポンプのゲージ、ケース類などの部品、フューエルフィラーアンダーパイプ、ＯＲＶＲホース、リザーブホース、ベントホースなどの各種燃料チューブ接続部品（コネクター等）、オイルチューブ接続部品、ブレーキホース接続部品、ウインドウオッシャー液用ノズル、冷却水、冷媒等用クーラーホース接続用部品、エアコン冷媒用チューブ接続用部品、消火器および消火設備用ホース、医療用冷却機材用チューブの接続用部品およびバルブ類、その他薬液およびガス搬送用チューブ用途に有効である。
【００７７】
以上のような薬液およびガスの耐透過性が必要とされる用途、自動車部品、内燃機関用途、電動工具ハウジング類などの機械部品を始め、電気・電子部品、医療、食品、家庭・事務用品、建材関係部品、家具用部品など各種用途に有効である。
【００７８】
【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。
【００７９】
［燃料透過係数］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℃で行った。）により１ｍｍ厚の円盤状試験片（直径６ｃｍ）を作成した。得られた試験片をＧＴＲ−３０ＸＡＴＫ（ヤナコ分析工業社製）に取り付けて、試験片上部のセルにモデルガソリン（（イ）トルエンとイソオクタンの体積比５０／５０の混合物と（ロ）エタノールを９０対１０重量比に混合したアルコールガソリン混合物）を仕込み、ＪＩＳ Ｋ７１２６ Ａ法（差圧法）に従って、測定温度６０℃で測定した。
【００８０】
［−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。
【００８１】
［−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。
【００８２】
［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。
【００８３】
［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ＡＳＴＭ１号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。
【００８４】
［耐透過性試験］射出成形（東芝機械社製ＩＳ１００ＦＩ−５Ａ、シリンダー温度２８５℃、金型温度８０℃）により、直径１２ｃｍ、厚み３ｍｍの半球形状の成形品を成形した。この成形品２個を熱板溶着法で接合して球状のモデル容器を得た。接合の前に片側の成形品には切削加工によって金属製注入口を装着した。このモデル容器（内容積約９００ｍｌ）にモデルガソリン（（トルエン／／イソオクタン＝５０／／５０体積％）とメタノールを８５対１５重量比に混合したアルコールガソリン混合物）５００ｍｌを金属製注入口より注入し、密封した。この後、６０℃の防爆オーブンで１０００時間処理した際の重量減量挙動からその透過性を評価した。重量減少量が０．５ｇ／日未満を合格と判定した。燃料減少量が０．５ｇ／日以上は不合格である
［落下試験］射出成形（東芝機械社製ＩＳ１００ＦＩ−５Ａ、シリンダー温度２８５℃、金型温度８０℃）により、直径１２ｃｍ、厚み３ｍｍの半球形状の成形品を成形した。この成形品２個を熱板溶着法で接合して球状のモデル容器を得た。接合の前に片側の成形品には切削加工によって金属製注入口を装着した。このモデル容器（内容積約９００ｍｌ）にトヨタ純正ＬＬＣ７００ｍｌを金属製注入口より注入し、密封した。この後、−４０℃の恒温槽に１２時間放置した後取り出し、直ちに高さ１ｍから自由落下させて破壊状態を観察し、下記の判定を行った。
○：割れや変形は認められない
△：変形やひび割れが生じ、内容物の漏洩が認められる
×：脆性的に破壊が発生し、内容物の漏洩が認められる
［モルホロジー観察］前記モデル容器の厚み方向の中心部から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。
【００８５】
［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１万倍で観察した任意のオレフィン系樹脂粒子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。
【００８６】
［実施例１〜８］、［比較例１〜７］
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。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。樹脂組成物の特性評価のために１２０℃で１晩除湿乾燥したペレットを用いて射出成形（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、燃料タンク、オイル用タンク、ラジエタータンク、各種薬剤用ボトルなどの薬液保存容器としての特性を評価するために、さらに射出成形（東芝機械社製ＩＳ１００ＦＩ−５Ａ、シリンダー温度２８５℃、金型温度８０℃）により、直径１２ｃｍ、厚み３ｍｍの半球形状の成形品を成形した。この成形品２個を熱板溶着法で接合して球状のモデル容器を得た。接合の前に片側の成形品には切削加工によって金属製注入口を装着した。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。実施例１〜１０が低温特性（柔軟性、耐衝撃性、落下試験）、燃料透過性、流動性、耐透過性等に優れ、極めて実用性が高く、ガソリンタンクに代表される薬液および／またはガスの搬送または貯蔵用の容器もしくはその付属部品として優れたものである。比較例１〜６においては低温特性、耐燃料透過性、流動性、耐透過性等に劣るものであった。
【００８７】
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。
【００８８】
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。
【００８９】
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／ｃｍ３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／ｃｍ３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。
［比較例８］
下記のＨＤＰＥを用いた他は、実施例と同様にして球状のモデル容器を得た。耐透過性に劣るため燃料タンク、オイル用タンク、ラジエタータンク、各種薬剤用ボトルなどの薬液保存容器としての使用に不適切なものであった。
ＨＤＰＥ：高密度ポリエチレン（三井化学（株）製”ハイゼックス”７０００Ｆ）
【００９０】
【表１】

【００９１】
【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、かつ薬液および／またはガスの耐透過性や成形性にも優れた薬液および／またはガスの搬送または貯蔵用の容器もしくはその付属部品が得られる。
【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 has a mechanical property, particularly a chemical solution having excellent flexibility and impact resistance under a low temperature atmosphere of −40 ° C., and also having excellent chemical solution and / or gas permeation resistance and moldability. The present invention relates to a container for transporting or storing gas or its accessory parts. In particular, a container for transporting or storing chemicals and / or gases having specific low-temperature impact properties, permeation resistance, and molding processability obtained by molding a resin composition comprising a polyester resin and a specific olefin resin, or It relates to the accessory parts.
[0002]
[Prior art]
Conventionally, high-density polyethylene (hereinafter abbreviated as HDPE), which is excellent in low-temperature impact resistance and chemical resistance and low in cost, has been applied to plastic automotive fuel parts such as gasoline tanks, hoses and valves. . However, HDPE has a problem that fuel permeability is large, and suppression of fuel scattering is required as part of environmental regulations.
[0003]
Recently, materials such as polyamide resin have been studied as materials having excellent fuel permeability, but they are inferior to HDPE in impact resistance, and there is a problem that permeation resistance is lowered with respect to alcohol-containing fuel. Examples of materials having excellent permeation resistance to alcohol-containing fuels include liquid crystal resins, polyester resins, polyphenylene sulfide resins (hereinafter abbreviated as PPS resins), polyacetal resins, and the like, but have the disadvantage of poor toughness and low-temperature impact resistance. Was.
[0004]
Many improvement methods have been proposed for improving the impact resistance of these resins. In particular, Patent Document 1 discloses a fuel excellent in fuel permeation resistance and impact resistance by using a PPS resin and an olefin resin. System parts are disclosed. However, PPS resins and liquid crystalline resins have higher material costs than HDPE, and the resulting parts are not economical enough.
[0005]
On the other hand, polyester resins represented by polyethylene terephthalate and polybutylene terephthalate are used for various electric / electronic parts, machine parts, automobile parts and the like because of their excellent characteristics.
[0006]
However, polyester resin is inferior in impact resistance. For this reason, many improvement methods have been proposed in the past, and among them, a method of blending a copolymer composed of monomers such as α-olefin and α, β-unsaturated glycidyl ester is frequently used. However, the molded products obtained by these methods show good impact resistance near room temperature, but the impact resistance comparable to that of HDPE cannot be obtained especially in a low temperature atmosphere of about -40 ° C. There is.
[0007]
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 2 and 3), a specific polyester resin with an ethylene / vinyl acetate system Improve impact resistance at low temperatures by blending a copolymer (see, for example, Patent Document 4), blending an impact-resistant component having an acid anhydride group and a specific glycidyl group-containing olefin copolymer Means for doing this (for example, see Patent Document 5) has been proposed.
[0008]
[Patent Document 1]
JP 2002-226707 A (Claim 1)
[0009]
[Patent Document 2]
Japanese Patent Publication No. 63-4466 (Claims)
[0010]
[Patent Document 3]
JP 2002-206052 A (Claim 1)
[0011]
[Patent Document 4]
Japanese Patent No. 3174339 (Claim 1)
[0012]
[Patent Document 5]
JP-A-2002-234992 (Claim 1)
[0013]
[Problems to be solved by the invention]
However, these conventionally proposed methods have not obtained a composition having an impact resistance of 500 J / m or more, which is comparable to that of HDPE, particularly in a low temperature atmosphere of −40 ° C. Therefore, when these compositions are used to produce containers and accessories for transporting and storing chemicals and / or gases, their impact at low temperatures is low and their use in extremely cold regions is limited. It is not practical as a general-purpose product. Accordingly, there is a demand for the development of a container for transporting or storing a chemical solution and / or gas or an accessory part thereof using a material that satisfies a higher degree of low temperature characteristics and is economically advantageous. The present invention can be used even in extremely cold regions by molding a resin composition that has superior flexibility and impact resistance in a low-temperature atmosphere than conventional materials, and is also excellent in permeation resistance and molding processability. It is an object of the present invention to provide a container for transporting or storing a chemical solution and / or gas, which can be used as a general-purpose product, and its accessory parts.
[0014]
[Means for Solving the Problems]
Therefore, the present inventors have studied to solve the above problems, and as a result, formed a specific morphology in a molded product obtained by processing a specific resin composition comprising a polyester resin (a) and an olefin resin (b). As a result, the inventors have found that the above-mentioned problems have been solved and that significant effects can be obtained, and the present invention has been achieved.
[0015]
That is, the present invention comprises the following items.
[0017]
(1) The amount of carboxyl end groups is 30-80 eq / tAt least one selected from polyethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate and copolymers thereof.60 to 95% by weight of the polyester resin (a), and 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 are added to the olefin polymer. Ethylene / α-olefin copolymer obtained by copolymerizing olefin copolymer (b-1) obtained by introducing a monomer component having ethylene and α-olefin having 3 to 20 carbon atoms ( a polyester resin composition comprising 5 to 40% by weight of an olefin resin (b) comprising b-2), the polyester resin (a) forms a continuous phase, and the olefin resin (b) is an average particle. A container for transporting or storing a drug solution and / or gas having a diameter of 0.01 to 2 [mu] m and dispersed, or an accessory thereof.
(2) The combined ratio of the functional group-containing olefin copolymer (b-1) and the ethylene / α-olefin copolymer (b-2) is such that the component (b-1) The container for transporting or storing a chemical solution and / or gas according to claim 1, wherein the component is 5 to 40% by weight and the component (b-2) is 60 to 95% by weight.
[0018]
  (3) The olefin copolymer (b-1) is an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefin polymer.OrA container for transporting or storing the chemical solution and / or gas according to (2) or an accessory thereof.
[0019]
  (4) In the above (3), the olefin copolymer (b-1) is a copolymer of ethylene and / or an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester. A container for transporting or storing the chemical solution and / or gas described above or an accessory thereof.
[0022]
(5) Tensile rupture elongation measured in accordance with ASTM-D638 at a temperature of −40 ° C. is 20 to 400%, Izod impact strength measured in accordance with ASTM-D256 is 500 to 2000 J / m, and toluene and isooctane are equivalent. Permeability coefficient at 60 ° C. is 50 g · mm / m in an alcohol gasoline mixture obtained by mixing a solution contained in a volume ratio and methanol in an 85 to 15 weight ratio²· The polyester resin composition having a length of 24 hr or less is formed, and the above (1) to (4) A container for transporting or storing the chemical solution and / or gas according to any one of the above or an accessory thereof.
[0023]
(6) The amount of carboxyl end groups of the polyester resin (a) is 35 to 70 eq / t, the tensile elongation at break is 20 to 400%, and the Izod impact strength is 500 to 2000 J / m. Characteristic said (5A container for transporting or storing a chemical solution and / or gas obtained by molding the resin composition as described in (1) or an accessory thereof.
[0024]
(7) The olefin resin (b) is dispersed in an average particle size of 0.01 to 2 μm.6) A container for transporting or storing the chemical solution and / or gas according to any one of the above or an accessory thereof.
(8) The chemical liquid and / or gas transport or storage container or its accessory parts for the chemical liquid and / or gas is a fuel system part for automobiles, or the chemical liquid and / or gas transport according to any one of the above (1) to (7) A storage container or accessory.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail based on embodiments.
[0026]
The polyester resin (a) 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.
[0029]
  In the present inventionUsePolyesterResin (a),polyethylene terephthalateTheLiethylene-2,6-naphthalenedicarboxylateAnd at least one polyester resin selected from these copolymers.
[0030]
  More preferably, polyethylene terephthalateTheReethylene-2,6-naphthalenedicarboxylate is exemplified, and polyethylene terephthalate is particularly preferable, but these polyester resins may be used as a mixture depending on necessary properties such as moldability, heat resistance, toughness, and surface property. It is suitable for practical use.
[0031]
The production method of the polyester resin (a) 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.
[0032]
When the direct polymerization method is used, first, an esterification reaction is performed to form an oligomer, and then a polycondensation reaction is performed to produce a polyester. 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.
[0033]
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.
[0034]
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.
[0035]
  In addition, the present inventionForIn order to obtain a polyester resin having a relatively large amount of carboxyl terminal groups of 30 to 80 eq / t (the amount of terminal groups per ton of polymer), it is preferable to set the polycondensation reaction time longer than before.
[0036]
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.
[0037]
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.
[0038]
The (b-1) olefin copolymer having at least one functional group selected from carboxylic acid group, carboxylic anhydride group, carboxylic acid ester group, carboxylic acid metal base and epoxy group used in the present invention is: It 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 acid 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.
[0039]
A monomer component having a functional group for introducing a functional group into an olefin polymer is a compound containing a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, an epoxy group, and the like. 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-dicarboxylic acid Examples thereof include unsaturated carboxylic acids such as acids, or carboxylic 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 aminoethyl methacrylate Propyl and the like.
[0040]
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.
[0041]
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.
[0042]
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.
[0043]
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.
[0044]
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.
[0045]
Further, 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.
[0046]
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.
[0047]
In the present invention, the olefin copolymer containing an epoxy group 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 an α, β-unsaturated carboxylic acid glycidyl ester as essential copolymerization components. 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.
[0048]
In the present invention, it is particularly preferable to use an olefin copolymer containing ethylene and a glycidyl ester of an α, β-unsaturated carboxylic acid as essential components. Among them, 60 to 99% by weight of ethylene and an α, β-unsaturated carboxylic acid are preferable. An olefin copolymer having 1 to 40% by weight of glycidyl ester as an essential copolymer component is particularly preferred.
[0049]
As the glycidyl ester of the α, β-unsaturated carboxylic acid,
[0050]
[Chemical 1]

[0051]
(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.
[0052]
  In the present inventionIs (b-2) An ethylene / α-olefin copolymer comprising ethylene and an α-olefin having 3 to 20 carbon atomsUseIt is a copolymer containing ethylene and one or more α-olefins having 3 to 20 carbon atoms as constituent components. 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 effect can be seen.
[0053]
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 the MFR is less than 0.01 g / 10 minutes, the fluidity is poor, and when it exceeds 70 g / 10 minutes, the impact strength may be lowered depending on the shape of the molded product.
[0054]
The production method of the olefinic resin (b) used in the present invention is not particularly limited, 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.
[0055]
The blending ratio of the polyester resin (a) and the olefin resin (b) of the present invention is 60 to 95% by weight of the polyester resin and 5 to 40% by weight of the olefin resin, preferably 70 to 85% by weight of the 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 permeation resistance of the polyester resin are impaired. In addition, the thickening at the time of melt-kneading increases, which is not preferable.
[0056]
  Furthermore, in the present invention, the functional group-containing olefin copolymer (b-1) and the ethylene / α-olefin copolymer (b-2) are used in combination as described above.. SoThe combined use ratio of the component (b-1) is 5 to 40% by weight, the component (b-2) is 60 to 95% by weight, and preferably the component (b-1) is 10 to 10% by weight. 30 weight% and (b-2) component are 70 to 90 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.
[0057]
The polyester resin composition used for the molding of the present invention can further contain an antioxidant or other additives as described below.
[0058]
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.
[0059]
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-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), n-octadecyl-3- (3,5-di-tert-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.
[0060]
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.
[0061]
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.
[0062]
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.
[0063]
Furthermore, it is possible to add resins other than the olefin resin to the polyester resin composition used in 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 used in the present invention, the inherent properties of the polyester resin are impaired, so that it is not preferred, and 10% by weight or less, more preferably 1% by weight or less is added.
[0064]
A container for transporting or storing a chemical solution and / or gas obtained by processing the polyester resin composition of the present invention or its accessory parts can be used by blending a filler as long as the effects of the present invention are not impaired. It is. 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 kou fiber, 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.
[0065]
The resin composition used for producing the container for transporting or storing the chemical solution and / or gas of the present invention or its accessory parts has a tensile elongation at break of 20 to 400 measured according to ASTM-D638 under the condition of a temperature of -40 ° C. %, And notched Izod impact strength measured according to ASTM-D256 is 500 to 2000 J / m, fuel ((toluene // isooctane = 50 // 50 vol%) and ethanol mixed in 90 to 10 weight ratio) Permeability coefficient of gasoline mixture) at 60 ° C is 50 g · mm / m²It is preferably 24 hr or less, more preferably, the tensile elongation at break is 30 to 400%, the notched Izod impact strength is 600 to 2000 J / m, and the fuel ((toluene // isooctane = 50 // 50 volume) %) And ethanol in a 90 to 10 weight ratio). The permeability coefficient at 60 ° C. is 30 g · mm / m.²-It is preferable that it is 24 hours or less. By processing the polyester resin composition having the above characteristics into a container for transporting or storing chemicals and / or gas or its accessory parts, for example, when used in an automobile gasoline tank, impact destructibility at the time of vehicle collision, etc. In addition to being excellent in the permeation resistance of gasoline, it is possible to obtain a very useful gasoline tank.
[0066]
Production of the polyester resin composition used in the present invention is carried out using a commonly known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll, and each component has a melting point of the polyester resin. A typical example is a method of kneading at the above processing temperature. Further, 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 relatively strengthen the shearing force applied to the resin melted and kneaded during the production of the resin composition. In addition, it is necessary to shorten the residence time during kneading. By combining these conditions, the polyester resin can be made into a continuous phase while preventing aggregation of the olefin copolymer in the resin composition, so that the olefin copolymer also aggregates during subsequent injection molding. This is because it is possible to prevent this, and the morphology of the present invention can be obtained. Specifically, using a twin screw extruder, the kneading temperature is the melting point of the polyester resin +0 to 20 ° C., and the residence time is 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.
[0067]
In order to obtain a high balance of flexibility and impact resistance at low temperatures, the container for transporting or storing the chemical solution and / or the gas of the present invention or its accessory parts is made of polyester resin 1 as shown in FIG. It is necessary to form a continuous phase (matrix) and the olefin resin 2 to form a dispersed phase (sea-island structure), and the average particle size of the olefin resin forming the dispersed phase is 0.01 to It is necessary from the viewpoint of low temperature characteristics, permeation resistance and fluidity that the polyester resin is dispersed at 2 μm, preferably 0.01 to 1 μm, and has a morphology in which the polyester resin 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 resin is in an agglomerated form and the average particle diameter is larger than 2 μm, it becomes difficult to obtain low temperature characteristics, and the permeation resistance tends to be lowered. Moreover, when polyester does not become a continuous phase, fluidity | liquidity and permeation resistance fall. In the case of the morphology of the present invention, the low temperature characteristics are excellent, and the permeation resistance and fluidity are particularly excellent.
[0068]
The average particle size here means that a model container is injection-molded at a processing temperature of the melting point of the polyester resin + 20 ° C., and a thin piece of 0.1 μm or less (about 80 nm) is cut from the central portion in the thickness direction to obtain transmission electron For the dispersion part of any 100 olefin-based resins observed with a microscope (magnification: 10,000 times), first, measure the maximum and minimum diameters, determine the average value, and then calculate the average value. The number average particle diameter.
[0069]
There are no particular restrictions on the processing method of the container for transporting or storing the chemical solution and / or gas of the present invention or its accessory parts, and a known method (injection molding, extrusion molding, blow molding, press molding, etc.) is used. However, the preferred method for production is injection molding. Injection molding refers to all those in which a polyester resin composition melted in a plasticizer is injected into a mold cavity under pressure and solidified in the mold to obtain a molded product. In addition to normal injection molding, For example, injection compression molding is also included. The processing temperature is usually selected from a temperature range higher than the melting point of the polyester resin + 5 to the melting point + 50 ° C. The molding method is generally a single layer, but it may be a multilayer by a two-color molding method.
[0070]
A preferable method for molding a container for transporting or storing a chemical solution and / or gas obtained by processing the polyester resin composition of the present invention or its accessory parts is to inject two or more divided bodies constituting the container or its accessory parts. It is a method of forming by forming and then joining them together. The method for joining the divided bodies is not particularly limited, and a known method (hot plate welding, vibration welding, injection welding, ultrasonic welding, laser welding, microwave welding) can be used.
[0071]
In the case of the hot plate welding method, the joining surfaces of the divided bodies are melted by a hot plate, and the joining surfaces of the divided bodies are quickly pressed to be welded. The hot plate conditions at this time may be normal conditions. For example, in the case of a contact method, a hot plate temperature of 230 to 350 ° C. and a melting time of 20 to 60 seconds can be employed.
[0072]
In the case of the vibration welding method, the joining surfaces of the divided bodies are brought into pressure contact with each other, and in this state, welding is performed by frictional heat generated by applying vibration in the lateral direction. The vibration conditions at this time may be normal conditions. For example, a vibration frequency of 100 to 300 Hz and an amplitude of 0.5 to 2.0 mm can be employed.
[0073]
In the case of the hot wire welding method, for example, the joining surfaces are pressed together in a state where an iron-chromium wire is embedded in the joining portion of the divided body, current is applied to the wire, Joule heat is generated, and the joining surface is welded by the generated heat.
[0074]
In the case of the injection welding method, after inserting the divided body into the mold or changing the position in the mold, hold the joined surfaces together, and newly inject molten resin to the periphery of the joined portion. Each divided body is welded together to form a hollow container. The injection welding conditions at this time may be normal conditions. For example, a resin temperature of 230 to 320 ° C., an injection pressure of 10 to 150 MPa, a mold clamping force of 100 to 4000 tons, and a mold temperature of 30 to 150 ° C. should be adopted. (The method of changing the position in the above-described mold is also called die slide molding or die rotation molding).
[0075]
In the case of the laser welding method, the laser beam is irradiated from the non-absorbing split body side in the state where the non-absorbing split body for laser light and the split body absorbing for laser light are superimposed on the bonding surface. And weld. Moreover, in order to make it laser-absorbability, the method of adding carbon black to the resin composition used for manufacture of this invention can be mention | raise | lifted. By adding carbon black, the transmittance of the irradiated laser beam can be reduced to 5% or less, and the energy of the laser beam can be efficiently converted into heat. The laser welding conditions at this time may be normal conditions. For example, a YAG laser, a laser beam wavelength of 800 to 1060 nm, and a laser beam output of 5 to 30 W can be adopted as the laser beam.
[0076]
The container for transporting or storing the chemical solution and / or gas of the present invention or its accessory parts are, for example, Freon-11, Freon-12, Freon-21, Freon-22, Freon-113, Freon-114, Freon-115. , Freon-134a, Freon-32, Freon-123, Freon-124, Freon-125, Freon-143a, Freon-141b, Freon-142b, Freon-225, Freon-C318, R-502, 1,1,1 -Trichloroethane, methyl chloride, methylene chloride, ethyl chloride, methyl chloroform, propane, isobutane, n-butane, dimethyl ether, castor oil based brake fluid, glycol ether brake fluid, borate ester brake fluid, brake fluid for extremely cold regions, Silicone oil brake fluid, mineral oil brake fluid, power Sealing oil, window washer fluid, long life coolant fluid (LLC fluid), gasoline, methanol, ethanol, iseptanol, butanol, nitrogen, oxygen, hydrogen, carbon dioxide, methane, propane, natural gas, argon, helium, xenon In addition, since the permeability of gases and / or liquids such as pharmaceutical agents and vaporized gases is low and excellent, it is effective for use in chemical storage containers such as fuel tanks, oil tanks, radiator tanks, and various chemical bottles. Also, valves and fittings such as cut-off valves attached to these tanks and bottles, parts such as attached pump gauges, cases, fuel filler underpipes, ORVR hoses, reserve hoses, vent hoses, and other fuel tube connection parts (Connectors, etc.), oil tube connection parts, brake hose connection parts, nozzles for window washer fluid, cooling water, refrigerant connection parts for cooler hoses, air conditioner refrigerant tube connection parts, fire extinguishers and fire extinguishing equipment hoses, medical It is effective for connecting parts and valves for tubes for cooling equipment, and other chemical and gas transport tubes.
[0077]
In addition to mechanical parts such as the above, where chemical and gas permeation resistance is required, automotive parts, internal combustion engines, power tool housings, etc., electrical / electronic parts, medical care, food, household / office supplies, It is effective for various applications such as building material parts and furniture parts.
[0078]
【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.
[0079]
[Fuel Permeability Coefficient] Injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C., except that the polybutylene terephthalate resin system was performed at a cylinder temperature 260 ° C. and a mold temperature 80 ° C. ) To produce a 1 mm-thick disc-shaped test piece (diameter 6 cm). The obtained test piece was attached to GTR-30XATK (manufactured by Yanaco Analytical Industrial Co., Ltd.), and model gasoline (a mixture of (a) toluene and isooctane in a 50/50 volume ratio and (b) ethanol was added to the cell at the top of the test piece. (Alcohol gasoline mixture mixed at a weight ratio of 10) was charged and measured at a measurement temperature of 60 ° C. according to JIS K7126 A method (differential pressure method).
[0080]
[−40 ° C. Izod Impact Strength] Notched Izod impact strength was measured according to ASTM-D256 except that the temperature atmosphere was −40 ° C.
[0081]
[−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.
[0082]
[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.
[0083]
[Minimum molding pressure] The minimum filling pressure when preparing an ASTM No. 1 test piece was determined by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C, mold temperature 130 ° C). However, the polybutylene terephthalate resin system was performed at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C.
[0084]
[Permeation Resistance Test] A hemispherical molded product having a diameter of 12 cm and a thickness of 3 mm was molded by injection molding (IS100FI-5A manufactured by Toshiba Machine Co., Ltd., cylinder temperature 285 ° C., mold temperature 80 ° C.). Two molded products were joined by a hot plate welding method to obtain a spherical model container. Prior to joining, a metal injection port was attached to the molded product on one side by cutting. 500 ml of model gasoline (alcohol gasoline mixture in which toluene // isooctane = 50 // 50% by volume) and methanol are mixed in an 85:15 weight ratio) is injected into this model container (with an internal volume of about 900 ml) from a metal inlet. And sealed. Thereafter, the permeability was evaluated from the weight loss behavior when treated in an explosion-proof oven at 60 ° C. for 1000 hours. A weight loss of less than 0.5 g / day was judged acceptable. The fuel reduction amount is over 0.5g / day
[Drop Test] A hemispherical molded product having a diameter of 12 cm and a thickness of 3 mm was formed by injection molding (IS100FI-5A manufactured by Toshiba Machine Co., Ltd., cylinder temperature 285 ° C., mold temperature 80 ° C.). Two molded products were joined by a hot plate welding method to obtain a spherical model container. Prior to joining, a metal injection port was attached to the molded product on one side by cutting. 700 ml of Toyota LLC was injected into this model container (with an internal volume of about 900 ml) from a metal inlet and sealed. Then, after leaving for 12 hours in a -40 degreeC thermostat, it took out, immediately dropped from 1 m in height, the destruction state was observed, and the following determination was performed.
○: No cracking or deformation
Δ: Deformation and cracking occur, leakage of contents is observed
×: Fracture occurs brittlely and leakage of contents is observed
[Morphological Observation] A thin piece of 0.1 μm or less was cut from the central portion of the model container in the thickness direction, observed with a transmission 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.
[0085]
[Average Particle Size] The average particle size of the olefin resin is measured using the image processing software “Scion Image” for a dispersed portion of 100 arbitrary olefin resin particles observed at a magnification of 10,000 as in the morphology 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 was obtained.
[0086]
  [Examples 1 to8], [Comparative Examples 1 to7]
  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. Further, as shown in Table 1, the following substances were added as necessary during the melt kneading as needed. Injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd. SG75H-MIV, cylinder temperature 280 ° C, mold temperature 130 ° C, polybutylene terephthalate resin system) Prepared a test piece with a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C.). In addition, in order to evaluate the characteristics of chemical storage containers such as fuel tanks, oil tanks, radiator tanks, and various chemical bottles, injection molding (IS100FI-5A manufactured by Toshiba Machine Co., Ltd., cylinder temperature 285 ° C., mold temperature) 80 ° C.), a hemispherical molded product having a diameter of 12 cm and a thickness of 3 mm was formed. Two molded products were joined by a hot plate welding method to obtain a spherical model container. Prior to joining, a metal injection port was attached to the molded product on one side by cutting. The results of measuring the low temperature characteristics and morphology of each sample are shown in Table 1. Examples 1 to 10 are excellent in low temperature characteristics (flexibility, impact resistance, drop test), fuel permeability, fluidity, permeation resistance, etc., extremely practical, and chemicals represented by gasoline tanks and / or It is an excellent container or accessory for transporting or storing gas. In Comparative Examples 1 to 6, the low temperature characteristics, fuel permeation resistance, fluidity, permeation resistance and the like were poor.
[0087]
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.
[0088]
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.
[0089]
    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.
[Comparative example8]
A spherical model container was obtained in the same manner as in the example except that the following HDPE was used. Since it is inferior in permeation resistance, it is unsuitable for use as a chemical solution storage container such as a fuel tank, an oil tank, a radiator tank, and various chemical bottles.
HDPE: High-density polyethylene ("Hi-X" 7000F manufactured by Mitsui Chemicals, Inc.)
[0090]
[Table 1]

[0091]
【The invention's effect】
According to the present invention, a chemical solution having excellent mechanical properties, particularly excellent flexibility and impact resistance under a low temperature atmosphere of −40 ° C., and excellent in chemical solution and / or gas permeation resistance and moldability, and A container for transporting or storing gas or its accessories 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 form a continuous phase together.
[Explanation of symbols]
1 Polyester resin
2 Olefin resin

Claims (8)

Weight carboxyl end groups Ri 30~80eq / t der, polyethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate and at least one polyester resin selected from these copolymers (a) 60 to 95 % By weight, and a monomer component 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 is introduced into the olefin polymer. Olefin copolymer (b-1) obtained by copolymerizing ethylene and α-olefin having 3 to 20 carbon atoms (b-2). The resin (b) is formed by molding a polyester resin composition of 5 to 40% by weight, and the polyester resin (a) has a continuous phase. A container for transporting or storing a chemical solution and / or gas, or an accessory part thereof, which is a morphology formed and dispersed in an olefin resin (b) having an average particle size of 0.01 to 2 μm. The combined ratio of the functional group-containing olefin copolymer (b-1) and the ethylene / α-olefin copolymer (b-2) is 5-40 in the component (b-1) with respect to the total of both. The container for transporting or storing a chemical solution and / or gas according to claim 1, wherein the component (b-2) is 60 to 95% by weight, or an accessory thereof. The olefin copolymer (b-1) is an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefin polymer. Containers or accessories for transporting or storing chemicals and / or gases. The chemical solution according to claim 3, wherein the olefin copolymer (b-1) is a copolymer of ethylene and / or an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester. / Or container for transporting or storing gas or its accessories. Tensile breaking elongation measured according to ASTM-D638 at a temperature of −40 ° C. is 20 to 400%, Izod impact strength measured according to ASTM-D256 is 500 to 2000 J / m, and toluene and isooctane have an equal volume. Molding the polyester resin composition having a permeation coefficient at 60 ° C. of 50 g · mm / m ² · 24 hr or less in an alcohol gasoline mixture in which a solution contained in a ratio and methanol are mixed at a weight ratio of 85 to 15 A container for transporting or storing a chemical solution and / or gas according to any one of claims 1 to 4 , or an accessory thereof. The carboxyl end group amount of the polyester resin (a) is 35 to 70 eq / t, the tensile elongation at break is 20 to 400%, and the Izod impact strength is 500 to 2000 J / m. A container for transporting or storing a chemical solution and / or gas obtained by molding the resin composition according to claim 5 or an accessory thereof. The container for transporting or storing a chemical solution and / or gas according to any one of claims 1 to 6 , wherein the olefin resin (b) has an average particle size of 0.01 to 2 µm. Or its accessories. The container for transporting or storing chemical liquid and / or gas or an accessory part thereof is a fuel system part for automobiles, or the container for transporting or storing chemical liquid and / or gas according to claim 1 or its Accessory parts.

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