JP2004346982A - Tube for fuel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tube for fuel having excellent alcohol and gasoline permeation preventing property, interlayer adhesiveness, and low temperature impact resistance. <P>SOLUTION: This tube for fuel comprises at least two layers having an (a) layer formed of polyundecaneamide (nylon 11) and/or polydoecaneamide (nylon 12) and a (b) layer formed of (B1) polyamide polymer meeting the requirement of an expression (1) and (B) laminar silicate containing polyamide composition in which (B2) laminar silica of 0.1 to 30 wt.% is uniformly distributed in the molecules of the polyamide polymer. 3.0 ≤ γB-γA ≤ 10.0 (1)γA (dyne/cm) indicates the surface tension of the polyundecaneamide (nylon 11) and/or the polydodecane amide (nylon 12), and γB (dyn/cm) indicates the surface tension of the polyamide polymer in the laminar silica containing polyamide composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００５２】
（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）の表面張力はそれぞれ、３４．９、３３．８（ｄｙｎｅ／ｃｍ）である。上記の表面張力の条件を満たすためには、（Ｂ）層状珪酸塩含有ポリアミド組成物中の（Ｂ１）ポリアミド重合体の表面張力は、例えば、ポリドデカンアミド（ナイロン１２）を使用した場合、３６．８≦γ_Ｂ ≦４３．８となる必要がある。よって、（Ｂ）層状珪酸塩含有ポリアミド組成物中の（Ｂ１）ポリアミド重合体を形成するポリアミド原料モノマーは、この表面張力の条件を満たすために、３員環以上のラクタム、アミノ酸、又はジアミンとジカルボン酸とからなるナイロン塩等の中から適宜決定される。
【００５３】
上記の表面張力の条件を満たすためには、カプロアミド、ドデカンアミド、ヘキサメチレンドデカミド、ドデカメチレンアジパミドからなる群より選ばれる少なくとも１種以上の反復構造単位を含むポリアミド重合体を挙げることができる。具体的には、ヘキサメチレンドデカミド重合体（ナイロン６１２）、ドデカメチレンアジパミド重合体（ナイロン１２６）、カプロアミド／ドデカンアミド共重合体（ナイロン６／１２共重合体）、カプロアミド／ヘキサメチレンドデカミド重合体（ナイロン６／６１２共重合体）、カプロアミド／ドデカメチレンアジパミド重合体（ナイロン６／１２６共重合体）、カプロアミド／ドデカンアミド／ヘキサメチレンドデカミド共重合体（ナイロン６／１２／６１２共重合体）等を挙げることができる。
【００５４】
上記の中でも、カプロアミド／ドデカンアミド共重合体（ナイロン６／１２共重合体）、及び／又はヘキサメチレンドデカミド重合体（ナイロン６１２）がさらに好ましい。また、（Ｂ１）ポリアミド重合体が共重合体である場合、カプロアミド、ドデカンアミド単位の組成比は、上記、表面張力の条件を満たすように、適宜決定することが可能である。さらに、上記、表面張力の条件を満たす限りにおいては、カプロアミド、ドデカンアミド単位の組成比の異なるカプロアミド／ドデカンアミド共重合体（ナイロン６／１２共重合体）の混合物でも構わない。
【００５５】
本発明において、（Ｂ）層状珪酸塩含有ポリアミド組成物中に含有される（Ｂ２）層状珪酸塩は局所的に凝集することなく、分子レベルで均一に分散し、珪酸塩層を形成している必要がある。ここで珪酸塩層とは、（Ｂ２）層状珪酸塩を構成する基本単位であり、（Ｂ２）層状珪酸塩が劈開されることにより得られるものである。ここで、（Ｂ２）層状珪酸塩とは、例えば一片が０．００２〜１μｍ、厚みが６〜２０Åの物質の一単位を示すものが好ましい。
【００５６】
ここでいう分子レベルで均一分散されるとは、前記（Ｂ２）層状珪酸塩が（Ｂ１）ポリアミド重合体中に分散される際に、それぞれが平均２０Å以上の層間距離を保っている状態をいう。ここで、層間距離とは（Ｂ２）層状珪酸塩の平板の重心間の距離を指し、分散されるとは（Ｂ２）層状珪酸塩の一枚一枚がもしくは平均的な重なりが５層以下の積層物が平行にあるいはランダムに、もしくは平行とランダムが混在した状態で、その５０重量％以上、好ましくは７０重量％以上が塊を形成することなく分散されている状態をいう。具体的には、（Ｂ）層状珪酸塩含有ポリアミド組成物の試験片について広角Ｘ線回折測定を行い、珪酸塩層の厚み方向に起因するピークが消失されていること、もしくは透過型電子顕微鏡写真撮影観察により、層状珪酸塩の塊がないことから確認することができる。
【００５７】
本発明で使用する（Ｂ２）層状珪酸塩の好ましい例としては、モンモリロナイト、バイデライト、サポナイト、ヘクトライト、ソーコナイト等のスメクタイト族、バーミキュライト等のバーミキュライト族、フッ素雲母、白雲母、パラゴナイト、金雲母、黒雲母、レピドライト等の雲母族、マーガライト、クリントナイト、アナンダイト等の脆雲母族、ドンバサイト、スドーアイト、クッケアイト、クリノクロア、シャモサイト、ニマイト等の緑泥石族などが挙げられる。
上記例示の（Ｂ２）層状珪酸塩は、天然のものであっても、合成あるいは変性されたものであってもよく、単独、あるいは数種を組合せて用いても構わない。
【００５８】
（Ｂ２）層状珪酸塩は、珪酸塩を主成分とする負に帯電した層とその層間に介在するイオン交換能を有する陽電荷（イオン）からなる構造を有するものである。
【００５９】
これらの（Ｂ２）層状珪酸塩の陽イオン交換容量（ＣＥＣ）が、５０〜２００ミリ当量／１００ｇ の範囲にあることが望ましい。陽イオン交換容量は、メチレンブルーの吸着量測定により求めることで測定される。この陽イオン交換容量が５０ミリ当量／１００ｇ未満のものでは、（Ｂ２）層状珪酸塩の分散劈開が十分に進行しない場合がある。一方、この陽イオン交換容量が ２００ミリ当量／１００ｇ を超えるものでは、層間の結合力が強固なため、（Ｂ２）層状珪酸塩の劈開が困難な場合がある。
【００６０】
特に陽イオン交換容量や入手容易性から、ベントナイトを精製して得られるモンモリロナイトが本発明には最適である。
【００６１】
モンモリロナイトは、次式で示されるもので、天然に産出するものを精製することにより得ることができる。Ｍ_ａ Ｓｉ_４ （Ａｌ_２−ａ Ｍｇ_ａ ）Ｏ_１０（ＯＨ）_２ ・ｎＨ_２ Ｏ（式中、Ｍはナトリウムのカチオンを表し、ａは０．２５〜０．６０である。また、層間のイオン交換性カチオンと結合している水分子の数は、カチオン種や湿度等の条件に応じて変わりうるので、これ以降、式中ではｎＨ２ Ｏで表す。）
またモンモリロナイトには次式群で表される、マグネシアンモンモリロナイト、鉄モンモリロナイト、鉄マグネシアンモンモリロナイトの同型イオン置換体も存在し、これらを用いてもよい。
Ｍ_ａ Ｓｉ_４ （Ａｌ_{１ ． ６７−ａ}Ｍｇ_{０ ． ５ ＋ ａ} ）Ｏ_１０（ＯＨ）_２ ・ｎＨ_２ Ｏ
Ｍ_ａ Ｓｉ_４ （Ｆｅ_２−ａ ^{３ ＋}Ｍｇ_ａ）Ｏ_１０（ＯＨ）_２ ・ｎＨ_２ Ｏ
Ｍ_ａ Ｓｉ_４ （Ｆｅ_{１ ． ６７−ａ} ^{３ ＋}Ｍｇ_{０ ． ５ ＋ ａ} ）Ｏ_１０（ＯＨ）_２ ・ｎＨ_２Ｏ
（式中、Ｍはナトリウムのカチオンを表し、ａは０．２５〜０．６０である。）
【００６２】
通常、モンモリロナイトは、その層間にナトリウムやカルシウム等のイオン交換性カチオンを有するが、その含有比率は産地によって異なる。本発明においては、イオン交換処理等によって層間のイオン交換性カチオンがナトリウムに置換されていることが必要である。また水ひ処理により精製したモンモリロナイトを用いることが好ましい。
【００６３】
また、本発明において、分散性をより向上させる目的で、前記（Ｂ２）層状珪酸塩の層間に、有機オニウムイオンを挿入（インターカレーション）した層状珪酸塩が、好適に用いられる。
【００６４】
有機オニウムイオンとは、アンモニウムイオン、ホスホニウムイオン、スルホニウムイオン、複素芳香環由来のオニウムイオン等に代表される構造を持つものである。これらのうち、入手容易性、安定性の観点からは、アンモニウムイオン、ホスホニウムイオン、複素芳香環由来のオニウムイオンが好適である。
【００６５】
アンモニウムイオンとしては、ヘキシルアンモニウム、オクチルアンモニウム、デシルアンモニウム、ドデシルアンモニウム、ヘキサデシルアンモニウム、オクタデシルアンモニウム等のアルキルアンモニウム、エタノールアミン、ｐ−アミノフェノール、ｍ−アミノフェノール等の水酸基を有する１級アミンのアンモニウム、グリシン、アラニン、バリン、ロイシン、イソロイシン、フェニルアラニン、チロシン、トレオニン、セリン、プロリン、トリプトファン、チロキシン、メチオニン、シスチン、システイン、アスパラギン、アスパラギン酸、グルタミン、グルタミン酸、リジン、アルギニン、ヒスチジン等のα−アミノ酸のアンモニウム、６−アミノカプロン酸、７−アミノヘプタン酸、８−アミノオクタン酸、９−アミノノナン酸、１０−アミノデカン酸、１１−アミノウンデカン酸、１２−アミノドデカン酸等のω−アミノ脂肪酸のアンモニウム等の１級アンモニウム類、メチルドデシルアンモニウム、ブチルドデシルアンモニウム、メチルオクタデシルアンモニウム等のジアルキルアンモニウム、ジエタノールアミン等の水酸基を有する２級アミンのアンモニウム等の２級アンモニウム類、ジメチルオクチルアンモニウム、ジメチルドデシルアンモニウム、ジメチルヘキサデシルアンモニウム、ジメチルオクタデシルアンモニウム等のトリアルキルアンモニウム、ジメチルフェニルアンモニウム、ジフェニルドデシルアンモニウム、ジフェニルオクタデシルアンモニウム等のフェニル基を有する３級アンモニウム、トリエタノールアミン等の水酸基を有する３級アミンのアンモニウム等の３級アンモニウム類、テトラエチルアンモニウム、テトラブチルアンモニウム、テトラオクチルアンモニウム等の同一のアルキル基を有する４級アンモニウム、トリメチルオクチルアンモニウム、トリメチルデシルアンモニウム、トリメチルドデシルアンモニウム、トリメチルテトラデシルアンモニウム、トリメチルヘキサデシルアンモニウム、トリメチルオクタデシルアンモニウム、トリメチルエイコサニルアンモニウム、トリメチルオクタデセニルアンモニウム、トリメチルオクタデカジエニルアンモニウム等のトリメチルアルキルアンモニウム、トリエチルドデシルアンモニウム、トリエチルテトラデシルアンモニウム、トリエチルヘキサデシルアンモニウム、トリエチルオクタデシルアンモニウム等のトリエチルアルキルアンモニウム、トリブチルドデシルアンモニウム、トリブチルテトラデシルアンモニウム、トリブチルヘキサデシルアンモニウム、トリブチルオクタデシルアンモニウム等のトリブチルアルキルアンモニウム、ジメチルジオクチルアンモニウム、ジメチルジデシルアンモニウム、ジメチルジドデシルアンモニウム、ジメチルジテトラデシルアンモニウム、ジメチルジヘキサデシルアンモニウム、ジメチルジオクタデシルアンモニウム、ジメチルジオクタデセニルアンモニウム、ジメチルジオクタデカジエニルアンモニウム等のジメチルジアルキルアンモニウム、ジエチルジドデシルアンモニウム、ジエチルジテトラデシルアンモニウム、ジエチルジヘキサデシルアンモニウム、ジエチルジオクタデシルアンモニウム等のジエチルジアルキルアンモニウム、ジブチルジドデシルアンモニウム、ジブチルジテトラデシルアンモニウム、ジブチルジヘキサデシルアンモニウム、ジブチルジオクタデシルアンモニウム等のジブチルジアルキルアンモニウム、メチルベンジルジヘキサデシルアンモニウム等のメチルベンジルジアルキルアンモニウム、ジベンジルジヘキサデシルアンモニウム等のジベンジルジアルキルアンモニウム、トリオクチルメチルアンモニウム、トリドデシルメチルアンモニウム、トリテトラデシルメチルアンモニウム等のトリアルキルメチルアンモニウム、トリオクチルエチルアンモニウム、トリドデシルエチルアンモニウム等のトリアルキルエチルアンモニウム、トリオクチルブチルアンモニウム、トリドデシルブチルアンモニウム等のトリアルキルブチルアンモニウム、トリメチルベンジルアンモニウム等の芳香環を有する４級アンモニウム、トリメチルフェニルアンモニウム等の芳香族アミン由来の４級アンモニウム等のイオンが挙げられる。
【００６６】
ホスホニウムイオンとしては、テトラブチルホスホニウム、テトラオクチルホスホニウム、トリメチルデシルホスホニウム、トリメチルドデシルホスホニウム、トリメチルヘキサデシルホスホニウム、トリメチルオクタデシルホスホニウム、トリブチルドデシルホスホニウム、トリブチルヘキサデシルホスホニウム、トリブチルオクタデシルホスホニウム等のアルキル４級ホスホニウム、フェニルトリメチルホスホニウム、フェニルトリブチルホスホニウム、ジフェニルジメチルホスホニウム、トリフェニルメチルホスホニウム、テトラフェニルホスホニウム等のフェニルアルキル４級ホスホニウム等の４級ホスホニウム類が、複素芳香環由来のオニウムイオンとしては、ピリジニウム、メチルピリジニウム、ジメチルピリジニウム、キノリニウム、イソキノリニウム等のイオンが挙げられる。また、上記は親水性を付与するために、エチレンオキサイド付加されたアンモニウムイオン、ホスホニウムイオンであってもよい。これらは複数種組み合わせて用いても良い。
【００６７】
これらの有機オニウムイオンのうち、比較的低分子量のもの、例えばヘキシルアンモニウム、オクチルアンモニウム、デシルアンモニウム等のアルキルアンモニウム、６−アミノカプロン酸、７−アミノヘプタン酸、８−アミノオクタン酸、９−アミノノナン酸、１０−アミノデカン酸、１１−アミノウンデカン酸、１２−アミノドデカン酸等のω−アミノ脂肪族カルボン酸のアンモニウム、バリン、ロイシン、イソロイシン、フェニルアラニン、チロシン、トレオニン、セリン、プロリン、ヒドロキシプロリン、トリプトファン、メチオニン、シスチン、システイン、アスパラギン酸、グルタミン酸、アスパラギン、グルタミン、リジン、アルギニン、ヒスチジン等のα−アミノ酸のアンモニウム等の１級アンモニウム類、ピリジニウム、メチルピリジニウム、ジメチルピリジニウム等の複素芳香環由来のオニウム類が好ましく、更に好ましくは、８−アミノオクタン酸、９−アミノノナン酸、１０−アミノデカン酸、１１−アミノウンデカン酸、１２−アミノドデカン酸等のω−アミノ脂肪族カルボン酸のアンモニウム、ピリジニウム等のイオンが、最も好ましくは１０−アミノデカン酸、１１−アミノウンデカン酸、１２−アミノドデカン酸等のω−アミノ脂肪族カルボン酸のアンモニウムイオンが使用される。
【００６８】
有機オニウムイオンの量は、（Ｂ２）層状珪酸塩の陽イオン交換容量に対し０．８〜２．０当量の範囲であれば特に制限はないが、通常０．９〜１．３当量程度となる。この量が０．８当量よりも少ないと、ポリアミド樹脂への分散性が低下し、２．０当量より多いと該オニウムイオン由来の遊離化合物が顕著となり、成形時の熱安定性低下、メヤニの発生、発煙、金型汚染、臭気等の原因となる場合がある。
【００６９】
有機オニウムイオンの（Ｂ２）層状珪酸塩の層間への挿入は、（Ｂ２）層状珪酸塩の懸濁液に該オニウムイオン又はこれを含む溶液を添加して、陽イオン交換を行わせることにより容易に達成される。含溶媒中での（Ｂ２）層状珪酸塩と有機オニウムイオンとの接触で簡便に行われる該オニウムイオンの層間への導入により、負に帯電した珪酸塩層の層間に有機構造を導入することができ、これによりポリアミド原料の層間への浸入と重合進行が促進され、（Ｂ２）層状珪酸塩の（Ｂ１）ポリアミド重合体への均一な分散が達成される。
【００７０】
有機オニウムイオンの（Ｂ２）層状珪酸塩の層間への挿入の際に用いる分散媒は、（Ｂ２）層状珪酸塩、有機オニウムイオン及び（Ｂ１）ポリアミド重合体の種類により適宜決定することができるが、層状珪酸塩を均一に分散させ、かつ膨潤化剤及びポリアミド重合体との相溶性がよいものが好ましい。
【００７１】
分散媒としては、水、メタノール、エタノール、プロパノール、イソプロパノール、エチレングリコール、ジエチレングリコール、１，４−ブタンジオール、グリセリン、ジメチルスルホキシド、ジメチルホルムアミド、酢酸、ギ酸、ピリジン、アニリン、フェノール、ニトロベンゼン、アセトニトリル、アセトン、メチルエチルケトン、クロロホルム、二硫化炭素、プロピレンカーボネート、２−メトキシエタノール、エーテル、四塩化炭素、ｎ−ヘキサン、カプロラクタム、ドデカンラクタム、６−アミノカプロン酸、１２−アミノドデカン酸などを例示することができる。分散媒は１種類又は２種類以上を用いることができる。特に、分散媒として水、メタノール、エタノール及び／又はカプロラクタムを用いることが好ましい。
【００７２】
本発明における（Ｂ２）層状珪酸塩の添加量は、０．１〜３０重量％が好ましく、０．５〜１０重量％がさらに好ましい。（Ｂ２）層状珪酸塩の添加量が０．１重量％未満の場合は、アルコールガソリン透過防止性が十分でなく、３０重量％より大きい場合は、燃料用チューブにおいて（Ｂ）層状珪酸塩ポリアミド組成物からなる層を薄くしても、チューブ成形が困難になるとともに、低温耐衝撃性や引張伸度が低下し好ましくない。
【００７３】
（Ｂ１）ポリアミド重合体に（Ｂ２）層状珪酸塩を均一に分散させる方法については、（１）（Ｂ２）層状珪酸塩を膨潤化剤と接触させ、予め層間を広げて層間にモノマー分子を取り込みやすくして後、（Ｂ１）ポリアミド重合体のポリアミド原料モノマーと混合し、重合する方法（特開昭６２−７４９５７号公報参照）、（２）分散媒中に（Ｂ２）層状珪酸塩が膨潤した状態で均一に分散された層状珪酸塩複合体を（Ｂ１）ポリアミド重合体と混合又は混練する方法（特開平２−３０５８２８号公報参照。）、（３）層状珪酸塩を高濃度で含む（Ｂ２）層状珪酸塩含有ポリアミド組成物を予め前記方法で調製し、この（Ｂ２）層状珪酸塩含有ポリアミド組成物と層状珪酸塩を含まない（Ｂ１）ポリアミド重合体を混合する方法を適用することができる。
【００７４】
本発明において使用される（Ｂ）層状珪酸塩含有ポリアミド組成物は、ＪＩＳＫ ６９２０に準じて測定した相対粘度が、１．５〜６．０、好ましくは２．０〜５．０、より好ましくは２．０〜４．５である。相対粘度が１．５より小さい場合、得られる燃料用チューブの機械的性質が低下する。また、６．０より大きくなると、溶融時の粘度が高くなり、チューブの成形が困難となる。
【００７５】
また、本発明において使用される（Ｂ）層状珪酸塩含有ポリアミド組成物には、必要に応じて、酸化防止剤、熱安定剤、紫外線吸収剤、光安定化剤、滑剤、無機質微粒子、帯電防止剤、難燃剤、結晶化促進剤、ガラス繊維、可塑剤、衝撃改良剤、導電性フィラー等を添加してもよい。
【００７６】
本発明に係わる燃料用チューブは、（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）からなる（ａ）層、及び下記式（１）の条件を満たす（Ｂ１）ポリアミド重合体とその分子中に（Ｂ２）層状珪酸塩０．１〜３０重量％が均一に分散された（Ｂ）層状珪酸塩含有ポリアミド組成物からなる（ｂ）層を含む、少なくとも２層から構成される。
【００７７】
３．０≦ γ_Ｂ −γ_Ａ ≦１０．０ （１）
（式中、γ_Ａ（ｄｙｎｅ／ｃｍ）は、（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）の表面張力、γ_Ｂ（ｄｙｎｅ／ｃｍ）は、（Ｂ）層状珪酸塩含有ポリアミド組成物中の（Ｂ１）ポリアミド重合体の表面張力を示す。）
【００７８】
本発明においては、（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）からなる（ａ）層、及び上記式（１）の条件を満たす（Ｂ１）ポリアミド重合体とその分子中に（Ｂ２）層状珪酸塩０．１〜３０重量％が均一に分散された（Ｂ）層状珪酸塩含有ポリアミド組成物からなる（ｂ）層を用いることにより、（ａ）層と（ｂ）層を接着層を介することなく直接積層することができるので、層数の増加によるコスト、管理面の煩雑さを抑えることができ、かつ、アルコールガソリン透過防止性、層間接着性、低温耐衝撃性に優れた燃料用チューブを得ることができる。
【００７９】
好ましい実施様態としては、（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）からなる（ａ）層、上記に記載した（Ｂ）層状珪酸塩含有ポリアミド組成物からなる（ｂ）層、及び（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）、又は（Ｃ）ポリカプロアミド（ナイロン６）からなる（ｃ）層を含む、少なくとも３層から構成される。
【００８０】
本発明の燃料用チューブにおいて、（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）からなる（ａ）層は、燃料用チューブの最外層と配置されることが好ましい。（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）からなる層が最外層に配置されないと道路の凍結防止剤により樹脂が劣化してしまう場合がある。
【００８１】
また、本発明の燃料用チューブにおいて、（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）、又は（Ｃ）ポリカプロアミド（ナイロン６）からなる（ｃ）層が燃料用チューブの最内層に配置すると、耐薬品性、衝撃性に優れ、経済的に有利な燃料用チューブを得ることが可能である。また、配管内を循環する燃料の内部摩擦あるいは管壁との摩擦によって発生したスパークが燃料に引火することを防止するため、導電性を有する（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）、又は（Ｃ）ポリカプロアミド（ナイロン６）からなる層が、最内層に配置されることが好ましい。その際、導電性を有しない（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）、又は（Ｃ）ポリカプロアミド（ナイロン６）からなる層が、前記導電層に対して外層側に配置されることにより、低温耐衝撃性、導電性を両立することが可能であり、また経済的にも有利である。
【００８２】
本発明の燃料用チューブにおいて、（Ｂ）層状珪酸塩含有ポリアミド組成物からなる（ｂ）層を含むことは必須であり、燃料用チューブの中間層に配置されることがより好ましい。（Ｂ）層状珪酸塩含有ポリアミド組成物からなる（ｂ）層が配置されないと燃料用チューブのアルコールガソリン透過防止性が悪くなる。
【００８３】
本発明の燃料用チューブでは、各層の厚さは特に制限されず、各層を構成する重合体の種類、燃料用チューブにおける全体の層数、用途などに応じて調節し得る。それぞれの層の厚みは、燃料用チューブのアルコールガソリン透過防止性、低温耐衝撃性、柔軟性等の特性を考慮して決定され、一般には、（ａ）層、（ｂ）層、（ｃ）層の厚さは、燃料用チューブ全体の厚みに対してそれぞれ３〜９０％が好ましい。アルコールガソリン透過防止性を考慮して、（ｂ）層の厚みは燃料用チューブ全体の厚みに対して、より好ましくは５〜８０％、さらに好ましくは１０〜５０％である。
【００８４】
また、本発明の燃料用チューブにおける全体の層数は特に制限されず、（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）からなる（ａ）層、（Ｂ）層状珪酸塩含有ポリアミド組成物からなる（ｂ）層の少なくとも２層を含み、好ましくは、（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）からなる（ａ）層、（Ｂ）層状珪酸塩含有ポリアミド組成物からなる（ｂ）層、及び（Ａ）ポリウンデカンアミド（ナイロン１１）及び／又はポリドデカンアミド（ナイロン１２）、又は（Ｃ）ポリカプロアミド（ナイロン６）からなる（ｃ）層を含む、少なくとも３層である限りはいずれでもよい。さらに本発明の燃料用チューブは、（ａ）層、（ｂ）層、（ｃ）層の３層以外に、他の熱可塑性樹脂からなる層を１層又は２層以上を有していてもよい。
【００８５】
他の熱可塑性樹脂としては、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンイソフタレート（ＰＥＩ）、ＰＥＴ／ＰＥＩ共重合体、ポリアリレート（ＰＡＲ）、ポリブチレンナフタレート（ＰＢＮ）、ポリエチレンナフタレート（ＰＥＮ）、液晶ポリエステル（ＬＣＰ）等のポリエステル系樹脂、ポリアセタール（ＰＯＭ）、ポリフェニレンオキシド（ＰＰＯ）等のポリエーテル系樹脂、ポリサルホン（ＰＳＦ）、ポリエーテルスルホン（ＰＥＳ）等のポリサルホン系樹脂、ポリフェニレンスルフィド（ＰＰＳ）、ポリチオエーテルサルホン（ＰＴＥＳ）等のポリチオエーテル系樹脂、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリアリルエーテルケトン（ＰＥＡＫ）等のポリケトン系樹脂、ポリアクリロニトリル（ＰＡＮ）、ポリメタクリロニトリル、アクリロニトリル／スチレン共重合体（ＡＳ）、メタクリロニトリル／スチレン共重合体、アクリロニトリル・ブダジエン・スチレン共重合体（ＡＢＳ）、メタクリロニトリル／スチレン／ブタジエン共重合体（ＭＢＳ）等のポリニトリル系樹脂、ポリメタクリル酸メチル（ＰＭＭＡ）、ポリメタクリル酸エチル（ＰＥＭＡ）等のポリメタクリレート系樹脂、ポリ酢酸ビニル（ＰＶＡｃ）等のポリ酢酸ビニル系樹脂、ポリ塩化ビニリデン（ＰＶＤＣ）、ポリ塩化ビニル（ＰＶＣ）、塩化ビニル／塩化ビニリデン共重合体、塩化ビニリデン／メチルアクリレート共重合体等のポリ塩化ビニル系樹脂、酢酸セルロース、酪酸セルロース等のセルロース系樹脂、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリフッ化ビニル（ＰＶＦ）、エチレン／テトラフルオロエチレン共重合体（ＥＴＦＥ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、エチレン／クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体（ＴＦＥ／ＨＦＰ，ＦＥＰ）、テトラフルオロエチレン／ヘキサフルオロプロピレン／ビニリデンフルオライド共重合体（ＴＦＥ／ＨＦＰ／ＶＤＦ，ＴＨＶ）、テトラフルオロエチレン／フルオロ（アルキルビニルエーテル）共重合体（ＰＦＡ）等のフッ素系樹脂、ポリカーボネート（ＰＣ）等のポリカーボネート系樹脂、熱可塑性ポリイミド（ＰＩ）、ポリアミドイミド（ＰＡＩ）、ポリエーテルイミド（ＰＥＩ）等のポリイミド系樹脂、熱可塑性ポリウレタン系樹脂、ポリエチレンアジパミド（ナイロン２６）、ポリテトラメチレンアジパミド（ナイロン４６）、ポリヘキサメチレンアジパミド（ナイロン６６）、ポリヘキサメチレンアゼパミド（ナイロン６９）、ポリヘキサメチレンセバカミド（ナイロン６１０）、ポリヘキサメチレンウンデカミド（ナイロン６１１）、ポリヘキサメチレンテレフタルアミド（ナイロン６Ｔ）、ポリヘキサメチレンイソフタルアミド（ナイロン６Ｉ）、ポリノナメチレンドデカミド（ナイロン９１２）、ポリノナメチレンテレフタラミド（ナイロン９Ｔ）、ポリデカメチレンドデカミド（ナイロン１０１２）、ポリデカメチレンテレフタラミド（ナイロン１０Ｔ）、ポリウンデカメチレンテレフタラミド（ナイロン１１Ｔ）、ポリドデカメチレンドデカミド（ナイロン１２１２）、ポリドデカメチレンテレフタラミド（ナイロン１２Ｔ）、ポリメタキシリレンアジパミド（ナイロンＭＸＤ６）、ポリトリメチルヘキサメチレンテレフタラミド（ＴＭＨＴ）、ポリビス（４−アミノシクロヘキシル）メタンドデカミド（ナイロンＰＡＣＭ１２）、ポリビス（３−メチル−４−アミノシクロヘキシル）メタンドデカミド（ナイロンジメチルＰＡＣＭ１２）やこれらを形成するポリアミド原料モノマーを数種用いた共重合体などのポリアミド系樹脂を挙げることができる。これらの中でも、ポリエステル系樹脂、ポリアミド系樹脂、ポリチオエーテル系樹脂、フッ素系樹脂が好ましく使用される。
【００８６】
また、熱可塑性樹脂以外の任意の基材、例えば、紙、金属系材料、無延伸、一軸又は二軸延伸プラスチックフィルム又はシート、織布、不織布、金属綿状、木質等を積層することも可能である。金属系材料としては、アルミニウム、鉄、銅、ニッケル、金、銀、チタン、モリブデン、マグネシウム、マンガン、鉛、錫、クロム、ベリリウム、タングステン、コバルトなどの金属や金属化合物及びこれら２種類以上からなるステンレス鋼などの合金鋼、アルミニウム合金、黄銅、青銅などの銅合金、ニッケル合金等の合金類などが挙げられる。
【００８７】
本発明の燃料用チューブの層数は２層以上であり、チューブ製造装置の機構から判断して８層以下、好ましくは３層〜７層、より好ましくは３層〜６層である。
【００８８】
本発明の燃料用チューブの外径は、燃料（例えばガソリン）の流量を考慮し、肉厚は燃料の透過性が増大せず、また、通常のチューブの破壊圧力を維持できる厚さで、かつ、チューブの組み付け作業容易性及び使用時の耐振動性が良好な程度の柔軟性を維持することができる厚さに設計され、限定されるものではない。好ましくは、外径は４〜３０ｍｍ、内径３〜２５ｍｍ、肉厚は０．０５〜５ｍｍである。
【００８９】
本発明の燃料用チューブの製造法としては、層の数もしくは材料の数に対応する押出機を用いて、溶融し押し出し、ダイ内あるいは外において同時に積層する方法（共押出法）、あるいは、一旦、単層チューブあるいは、上記の方法により製造された積層チューブを予め製造しておき、外側に順次、必要に応じては接着剤を使用し、樹脂を一体化せしめ積層する方法（コーティング法）を挙げることができる。
【００９０】
また、本発明の燃料用チューブが複雑な形状である場合や、成形後に加熱曲げ加工を施して成形品とする場合には、成形品の残留歪みを除去するために、上記の燃料用チューブを形成した後、前記チューブを構成する樹脂の融点のうち最も低い融点未満の温度で、０．０１〜１０時間熱処理して目的の成形品を得る事も可能である。
【００９１】
本発明の燃料用チューブにおいては、その途中に波形領域を有するものであってもよい。このような波形領域とは、チューブ本体途中の適宜の領域を、波形形状、蛇腹形状、アコーディオン形状、又はコルゲート形状等に形成した領域である。
かかる波形の折り目が複数個環状に配設されている領域を有することにより、その領域において環状の一側を圧縮し、他側を外方に伸張することができるので、応力疲労や層間の剥離を伴うことなく容易に任意の角度で曲げることが可能になる。
【００９２】
本発明の燃料用チューブの波形領域は、まず直管状のチューブを成形した後に、引き続いてモールド成形し、所定の波形形状等とすることにより容易に形成することができる。なお、本発明の燃料用チューブは、その全長にわたって波形領域を有するものだけでなく、部分的に波形領域を有するものであっても良い。
【００９３】
このように成形した燃料用チューブの外周の全部又は一部には、石ハネ、他部品との摩耗、耐炎性を考慮してエピクロルヒドリンゴム、ＮＢＲ、ＮＢＲとポリ塩化ビニルの混合物、クロロスルホン化ポリエチレンゴム、塩素化ポリエチレンゴム、アクリルゴム（ＡＣＭ）、クロロプレンゴム（ＣＲ）、エチレン−プロピレンゴム（ＥＰＲ）、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）、ＮＢＲとＥＰＤＭの混合物ゴム、塩化ビニル系、オレフィン系、エステル系、アミド系等の熱可塑性エラストマー等から構成するソリッド又はスポンジ状の保護部材（プロテクター）を配設することができる。保護部材は既知の手法によりスポンジ状の多孔体としてもよい。多孔体とすることにより、軽量で断熱性に優れた保護部を形成できる。また、材料コストも低減できる。あるいは、ガラス繊維などを添加してその強度を改善してもよい。保護部材の形状は特に限定されないが、通常は、筒状部材又は燃料用チューブを受け入れる凹部を有するブロック状部材である。筒状部材の場合は、予め作製した筒状部材に燃料用チューブを後で挿入したり、あるいは燃料用チューブの上に筒状部材を被覆押出しして両者を密着して作ることができる。両者を接着させるには、保護部材内面あるいは前記凹面に必要に応じ接着剤を塗布し、これに燃料用チューブを挿入又は嵌着し、両者を密着することにより、燃料用チューブと保護部材の一体化された構造体を形成する。
【００９４】
かくして得られた本発明の燃料用チューブは、アルコールガソリン透過防止性、層間接着性、低温耐衝撃性等に優れている。したがって、上記特性が十分に発揮される、ガソリン、灯油、ディーゼルガソリン、メタノール、エタノール、プロパノール、ブタノール、含アルコールガソリン、メチル−ｔ−ブチルエーテル、含酸素ガソリン、含アミンガソリン、サワーガソリン等の燃料用チューブ、具体的には、フィードチューブ、リターンチューブ、エバポチューブ、フューエルフィラーチューブ、ＯＲＶＲチューブ、リザーブチューブ、ベントチューブ等を挙げることができる。特に、自動車燃料用チューブとして好ましい。
【００９５】
【実施例】
以下に実施例及び比較例を示し、本発明を具体的に説明するが、本発明はこれに限定されるものではない。
なお、実施例及び比較例における物性測定は次のように行った。
【００９６】
（相対粘度）
ＪＩＳ Ｋ６９２０に準じて、９６％の硫酸中、ポリアミド濃度１％、温度２５℃の条件下で測定した。
【００９７】
（表面張力）
三菱総合研究所製のソフトウェア「高分子材料設計支援システム ＥＸＰＯＤ」を使用し、前記の式により求めた。
【００９８】
（物性評価）
（低温耐衝撃性）
ＳＡＥ Ｊ２２６０に記載の方法で評価した。
【００９９】
（アルコールガソリン透過防止性）
積層チューブを２０ｃｍ長に切断したものを試料として使用する。試料を１１０℃×２ｈｒ乾燥し、質量測定を行った後、これにＦｕｅｌＣ（イソオクタン／トルエン＝５０／５０体積比）とエタノールを９０／１０体積比に混合したアルコール／ガソリン（以下、ＣＥ１０と称す場合がある）を封入して両端を密封する。これを６０℃の恒温槽内にセットし、２４ｈｒ毎にホースを取り出し、室温に戻ったところで重量測定を行う。１日あたりの重量変化をチューブ１ｍあたりの内層表面積で除して燃料透過係数（ｇ／ｍ^２・ｄａｙ）を算出する。
【０１００】
（層間接着性）
積層チューブを２０ｃｍ長に切断し、それをさらに縦に切断したものをテストピースとして使用する。外層と内層を端から１ｃｍ強制的に剥離し、使用機器としてテンシロン万能試験機を用いて、外層と内層をはさみ、５０ｍｍ／ｍｉｎの引張速度で、１８０℃剥離試験を行う。Ｓ−Ｓカーブの極大点から最高強度を読み取り、層間接着強度（Ｎ／ｃｍ）とする。
【０１０１】
［実施例及び比較例で用いた材料］
（Ａ）ナイロン１２
（Ａ−１）ナイロン１２樹脂組成物の製造
ＵＢＥＳＴＡ３０３０Ｕ（宇部興産製、相対粘度２．２７、表面張力３３．８ｄｙｎｅ／ｃｍ）に衝撃改良材として、ＪＳＲ Ｔ７７１２ＳＰ（ＪＳＲ製）をあらかじめ混合し、二軸溶融混練機（（株）日本製鋼所製、型式：ＴＥＸ４４）に供給する一方、該二軸溶融混練機のシリンダーの途中から、可塑剤として、ベンゼンスルホン酸ブチルアミドを定量ポンプにより注入し、シリンダー温度１８０〜２６０℃で溶融混練し、溶融樹脂をストランド状に押出した後、これを水槽に導入し、冷却、カット、真空乾燥して、ナイロン１２樹脂８５重量％、衝撃改良材１０重量％、可塑剤５重量％よりなるナイロン１２樹脂組成物のペレットを得た（以下このナイロン樹脂組成物を（Ａ−１）という）。
【０１０２】
（Ａ−２）ナイロン１２樹脂組成物の製造
上記（Ａ−１）の製造法において、ＵＢＥＳＴＡ３０３０ＵをＵＢＥＳＴＡ３０２０Ｕ（宇部興産製、相対粘度１．８６、表面張力３３．８ｄｙｎｅ／ｃｍ）に変更し、導電性フィラーとしてケッチェンブラックＥＣ６００ＪＤ（アクゾノーベル製）を用い、可塑剤を用いない以外は同様にして、ナイロン１２樹脂７３重量％、衝撃改良材２０重量％、導電性フィラー７％重量よりなるナイロン１２樹脂組成物のペレットを得た（以下このナイロン樹脂組成物を（Ａ−２）という）。
【０１０３】
（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物
（Ｂ−１）層状珪酸塩含有ポリアミド樹脂組成物の製造
層状珪酸塩の一単位の厚みが平均的に９．５Åで、一辺の長さが約０．１μｍのモンモリロナイト１００ｇを２．３リットルの水に分散させ、これに２８．１ｇの１２−アミノドデカン酸と１２ｍｌの濃塩酸を加え、８０℃で６０分間攪拌した。さらに、十分洗浄したものを、ブフナーロートを用いて吸引濾過を行い、含水状態の複合物（以下１２ＭＭＴと略す。）を得た。この複合物の一部を採取し、水分量を求めたところ８８％であった。なお、１２−アミノドデカン酸とモンモリロナイトとの複合物（１２ＭＭＴ）の層間距離をＸ線回折により測定したところ、１８Åであった。
次に、この１２ＭＭＴに水及びカプロラクタムをその比率が、１：９：９になるように加えて攪拌、混合した。
この後、ナイロン６／１２共重合体（ＵＢＥ Ｎｙｌｏｎ ７０３４Ｂ、宇部興産（株）製、相対粘度３．９）９８重量部に対して、前記１２−アミノドデカン酸モンモリロナイトとの複合物（１２ＭＭＴ）に、さらに水及びカプロラクタムを加えた１２ＭＭＴ複合体３８重量部を、、二軸溶融混練機（（株）日本製鋼所製、型式：ＴＥＸ４４）に供給し、シリンダー温度２１０〜２５０℃で溶融混練し、溶融樹脂をストランド状に押出した後、これを水槽に導入し、冷却、カット、ナイロン６／１２共重合体及び複合体からなるペレットを得た。このペレットを熱水中に浸漬し、前記１２ＭＭＴ中の分散媒の一つであるカプロラクタムを除去した後、真空乾燥して、層状珪酸塩含有ポリアミド組成物を得た（層状珪酸塩含有率２．０重量％、相対粘度３．３、表面張力４２．９ｄｙｎｅ／ｃｍ、以下この組成物を（Ｂ−１）という）。
【０１０４】
（Ｂ−２）層状珪酸塩含有ポリアミド樹脂組成物の製造
上記、（Ｂ−１）層状珪酸塩含有ポリアミド樹脂組成物の製造において、ナイロン６／１２共重合体（ＵＢＥ Ｎｙｌｏｎ ７０３４Ｂ、相対粘度３．９）を、ナイロン６１２（ＺＹＴＥＬ １５８ Ｄｏｐｏｎｔ（株）製 相対粘度２．４）に変えた以外は同様にして、層状珪酸塩含有ポリアミド組成物を得た（層状珪酸塩含有率２．０重量％、相対粘度２．１、表面張力３７．７ｄｙｎｅ／ｃｍ、以下この組成物を（Ｂ−２）という）。
【０１０５】
（Ｂ−３）層状珪酸塩含有ポリアミド樹脂組成物の製造
上記、（Ｂ−１）層状珪酸塩含有ポリアミド樹脂組成物の製造において、ナイロン６／１２共重合体（ＵＢＥ Ｎｙｌｏｎ ７０３４Ｂ、相対粘度３．９）を、ナイロン６／６６共重合体（ＵＢＥ Ｎｙｌｏｎ ５０３４Ｂ、相対粘度４．１）に変えた以外は同様にして、層状珪酸塩含有ポリアミド組成物を得た（層状珪酸塩含有率２．０重量％、相対粘度３．４、表面張力４５．２ｄｙｎｅ／ｃｍ、以下この組成物を（Ｂ−３）という）。
【０１０６】
（Ｂ−４）層状珪酸塩含有ポリアミド樹脂組成物の製造
上記、（Ｂ−１）層状珪酸塩含有ポリアミド樹脂組成物の製造において、ナイロン６／１２共重合体（ＵＢＥ Ｎｙｌｏｎ ７０３４Ｂ、相対粘度３．９）を、ナイロン６／１２共重合体（ＵＢＥ Ｎｙｌｏｎ ７１２５Ｕ、相対粘度２．４）に変えた以外は同様にして、層状珪酸塩含有ポリアミド組成物を得た（層状珪酸塩含有率２．０重量％、相対粘度２．０、表面張力３６．６ｄｙｎｅ／ｃｍ、以下この組成物を（Ｂ−４）という）。
【０１０７】
（Ｃ）ナイロン６
（Ｃ−１）ナイロン６樹脂組成物の製造
ＵＢＥ Ｎｙｌｏｎ１０２４Ｂ（宇部興産製、相対粘度３．５０）に衝撃改良材として、ＪＳＲ Ｔ７７１２ＳＰ（ＪＳＲ製）をあらかじめ混合し、二軸溶融混練機（（株）日本製鋼所製、型式：ＴＥＸ４４）に供給する一方、該二軸溶融混練機のシリンダーの途中から、可塑剤として、ベンゼンスルホン酸ブチルアミドを定量ポンプにより注入し、シリンダー温度２３０〜２７０℃で溶融混練し、溶融樹脂をストランド状に押出した後、これを水槽に導入し、冷却、カット、真空乾燥して、ナイロン６樹脂 ７５重量％、衝撃改良材１０重量％、可塑剤 １５重量％よりなるナイロン６樹脂組成物のペレットを得た（以下このナイロン樹脂組成物を（Ｃ−１）という）。
【０１０８】
（Ｃ−２）ナイロン６樹脂組成物の製造
上記（Ｃ−１）の製造法において、ＵＢＥ Ｎｙｌｏｎ１０２４Ｂを１０１５Ｂ（宇部興産製、相対粘度２．６４）に変更し、導電性フィラーとしてケッチェンブラックＥＣ６００ＪＤ（アクゾノーベル製）を用いる以外は同様にして、ナイロン６樹脂６０重量％、衝撃改良材３０重量％、可塑剤５重量％、導電性フィラー５％重量よりなるナイロン６樹脂組成物のペレットを得た（以下このナイロン樹脂組成物を（Ｃ−２）という）。
【０１０９】
（Ｄ）変性ポリオレフィン
（Ｄ−１）マレイン酸変性ポリプロピレン 三井化学（株）製 Ａｄｍｅｒ ＱＦ５００
【０１１０】
実施例１
上記に示す（Ａ）ナイロン１２樹脂組成物（Ａ−１）、（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物（Ｂ−１）、（Ｃ）ナイロン６樹脂組成物（Ｃ−１）とを使用して、Ｐｌａｂｏｒ製３層チューブ成形機にて、（Ａ）を押出温度２５０℃、（Ｂ）を押出温度２６０℃、（Ｃ）を押出温度２６０℃にて別々に溶融させ、吐出された溶融樹脂をアダプターによって合流させ、管状に成形し、寸法制御するサイジングダイにより冷却し、引き取りを行い、（Ａ）ナイロン１２樹脂組成物からなる層を（ａ）層、（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物からなる層を（ｂ）層、（Ｃ）ナイロン６樹脂組成物からなる層を（ｃ）層としたとき、層構成が（ａ）／（ｂ）／（ｃ）＝０．３５／０．３０／０．３５ｍｍ、内径６ｍｍ、外径８ｍｍの積層チューブを得た。当該積層チューブの物性測定結果を表１に示す。
【０１１１】
実施例２
実施例１において、（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物（Ｂ−１）を（Ｂ−２）に変えた以外、実施例１と同様にして、表１に示す層構成の積層チューブを得た。当該積層チューブの物性測定結果を表１に示す。
【０１１２】
実施例３
実施例１において、（Ｃ）ポリアミド６樹脂組成物（Ｃ−１）を（Ｃ−２）に変え、（Ｃ）を押出温度２７０℃にて溶融させた以外、実施例１と同様にして、表１に示す層構成の積層チューブを得た。当該積層チューブの物性測定結果を表１に示す。また、当該積層チューブの導電性をＳＡＥ Ｊ−２２６０に準拠して測定したところ、１０^６Ω／ｓｑｕａｒｅ以下であり、静電気除去性能に優れていることを確認した。
【０１１３】
実施例４
実施例１において、（Ｃ）ポリアミド６樹脂組成物（Ｃ−１）を（Ａ）ナイロン１２樹脂組成物（Ａ−１）に変えた以外、実施例１と同様にして、表１に示す層構成の積層チューブを得た。当該積層チューブの物性測定結果を表１に示す。
【０１１４】
実施例５
実施例１において、（Ｃ）ポリアミド６樹脂組成物（Ｃ−１）を（Ａ）ナイロン１２樹脂組成物（Ａ−２）に変え、（Ａ）を押出温度２７０℃にて溶融させた以外、実施例１と同様にして、表１に示す層構成の積層チューブを得た。当該積層チューブの物性測定結果を表１に示す。
【０１１５】
実施例６
上記に示す（Ａ）ナイロン１２樹脂組成物（Ａ−１）、（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物（Ｂ−１）、（Ｃ）ナイロン６樹脂組成物（Ｃ−１）、（Ｃ−２）とを使用して、Ｐｌａｂｏｒ製４層チューブ成形機にて、（Ａ）を押出温度２６０℃、（Ｂ）を押出温度２６０℃、（Ｃ）を押出温度２７０℃にて別々に溶融させ、吐出された溶融樹脂をアダプターによって合流させ、管状に成形し、寸法制御するサイジングダイにより冷却し、引き取りを行い、（Ａ）ナイロン１２樹脂組成物からなる層を（ａ）層、（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物からなる層を（ｂ）層、（Ｃ）ナイロン６樹脂組成物（Ｃ−１）からなる層を（ｃ）層、（Ｃ）ナイロン６樹脂組成物（Ｃ−２）からなる層を（ｃ’）層としたとき、層構成が（ａ）／（ｂ）／（ｃ）／（ｃ’）＝０．４０／０．３０／０．２０／０．１０ｍｍ、内径６ｍｍ、外径８ｍｍの積層チューブを得た。当該積層チューブの物性測定結果を表１に示す。また、当該積層チューブの導電性をＳＡＥ Ｊ−２２６０に準拠して測定したところ、１０^６Ω／ｓｑｕａｒｅ以下であり、静電気除去性能に優れていることを確認した。
【０１１６】
実施例７
実施例６において、（Ｃ）ナイロン６樹脂組成物（Ｃ−１）、（Ｃ−２）を（Ａ）ナイロン１２樹脂組成物（Ａ−１）、（Ａ−２）に変えた以外は、実施例６と同様にして、（Ａ）ナイロン１２樹脂組成物（Ａ−１）からなる層を（ａ）層、（Ａ）ナイロン１２樹脂組成物（Ａ−２）からなる層を（ａ’）層、（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物からなる層を（ｂ）層としたとき、層構成が（ａ）／（ｂ）／（ａ）／（ａ’）＝０．４０／０．３０／０．２０／０．１０ｍｍ、内径６ｍｍ、外径８ｍｍの積層チューブを得た。当該積層チューブの物性測定結果を表１に示す。また、当該積層チューブの導電性をＳＡＥ Ｊ−２２６０に準拠して測定したところ、１０^６Ω／ｓｑｕａｒｅ以下であり、静電気除去性能に優れていることを確認した。
【０１１７】
比較例１
実施例１において、（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物（Ｂ−１）、（Ｃ）ナイロン６樹脂組成物（Ｃ−１）を使用しない以外は、実施例１と同様にして、表１に示す単層チューブを得た。当該単層チューブの物性測定結果を表１に示す。
【０１１８】
比較例２
実施例１において、（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物（Ｂ−１）を（Ｄ）変性ポリオレフィン（Ｄ−１）に変え、（Ｄ）を押出温度１９０℃にて溶融させた以外は、実施例１と同様にして、表１に示す層構成の積層チューブを得た。当該積層チューブの物性測定結果を表１に示す。
【０１１９】
比較例３
実施例１において、（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物（Ｂ−１）を（Ｂ−３）に変えた以外は、実施例１と同様にして、表１に示す層構成の積層チューブを得た。当該積層チューブの物性測定結果を表１に示す。
【０１２０】
比較例４
実施例１において、（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物（Ｂ−１）を（Ｂ−４）に変えた以外は、実施例１と同様にして、表１に示す層構成の積層チューブを得た。当該積層チューブの物性測定結果を表１に示す。
【０１２１】
比較例５
実施例１において、（Ｂ）層状珪酸塩含有ポリアミド樹脂組成物（Ｂ−１）を（Ｂ−４）に、（Ｃ）ナイロン６樹脂組成物（Ｃ−１）を（Ａ）ナイロン１２樹脂組成物（Ａ−１）に変えた以外は、実施例１と同様にして、表１に示す層構成の積層チューブを得た。当該積層チューブの物性測定結果を表１に示す。
【０１２２】
【表１】

【０１２３】
【発明の効果】
本発明の燃料用チューブは、耐熱性、耐薬品性、低温耐衝撃性、アルコールガソリン透過防止性、層間接着性に優れている。特に自動車用燃料用チューブとして好適である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polyamide resin (nylon 11, 12 or the like), a polyamide polymer satisfying a specific surface tension condition, and a layered silicate-containing polyamide composition in which a layered silicate layered silicate is uniformly dispersed in its molecule. TECHNICAL FIELD The present invention relates to a fuel tube having a layer formed of a fuel gas, and particularly to a fuel tube having excellent alcohol gasoline permeation resistance, interlayer adhesion, and low-temperature impact resistance.
[0002]
[Prior art]
In the past, automobile tubing tubes have been subject to the problem of rust caused by antifreezing agents on roads, and in recent years, in response to the demand for energy saving, which is an urgent issue in the prevention of global warming, the main material is metal. An alternative to resin, which is excellent in rust prevention and lightweight, is being advanced. Examples of the resin used as the piping tube include a polyamide resin, a saturated polyester resin, a polyolefin resin, a thermoplastic polyurethane resin, and the like. In addition, the applicable range was limited due to insufficient chemical resistance and the like.
[0003]
On the other hand, a gasoline fuel containing an alcohol such as ethanol or methanol, an aromatic compound, or an ether such as methyl-t-butyl ether (MTBE) is transferred to the automobile piping tube. In recent years, from the viewpoint of environmental protection, regulations on gasoline fuel permeation, which is a cause of air pollution from the automobile piping tube, are becoming more stringent. Under such strict regulations, conventionally used polyamide resins, particularly nylon 11 and / or nylon 12, which are excellent in strength, toughness, chemical resistance and flexibility, are used alone (single layer). The above-mentioned tubes do not have sufficient permeation-preventing properties for the fuel described above, and are particularly required to be improved in alcohol-gasoline permeation-preventing properties.
[0004]
For this reason, it is necessary to increase the wall thickness in order to improve the alcohol gasoline permeation prevention property. However, this has the disadvantage that the flexibility of the piping is reduced or heavier, and the cost is reduced in terms of materials and productivity. There was a problem of getting high.
[0005]
As a solution to this, a fuel tube using a polyamide resin composition containing a layered silicate uniformly dispersed has been proposed, but even a fuel tube using this resin does not have sufficient alcohol gasoline permeation prevention properties. It could not be said (see Patent Document 1). Further, three or more layers composed of (A) a layer composed of nylon 11 resin and / or nylon 12, (B) a layer composed of nylon 6, and (C) a layer composed of a polyamide composition containing a layered silicate dispersed uniformly. (See Patent Document 2). However, in the fuel tube, a modified polyolefin resin or the like is used as an adhesive resin, which may lead to complicated cost and management due to an increase in the number of layers.
[0006]
[Patent Document 1]
JP-A-5-293916
[Patent Document 2]
JP 2001-31482 A
[0007]
[Problems to be solved by the invention]
An object of the present invention is to solve the above problems and to provide a fuel tube excellent in alcohol gasoline permeation prevention properties, interlayer adhesion properties, and low-temperature impact resistance.
[0008]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that a layer composed of nylon 11 and / or nylon 12, a polyamide polymer satisfying a specific surface tension condition, and a layered silicate in its molecule. A fuel tube made by laminating layers of a layered silicate-containing polyamide composition in which is uniformly dispersed has both interlayer adhesion and alcohol gasoline permeation prevention properties, low-temperature impact resistance, heat resistance, chemical resistance, etc. Have been found to satisfy various characteristics.
[0009]
That is, the present invention
(A) a layer (a) composed of polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), and (B1) a polyamide polymer satisfying the following formula (1) and (B2) The present invention relates to a fuel tube having at least two layers (b) composed of a layered silicate-containing polyamide composition in which 0.1 to 30% by weight of a layered silicate is uniformly dispersed. is there.
[0010]
3.0 ≦ γ_B  −γ_A  ≦ 10.0 (1)
(Where γ_A(Dyne / cm) is the surface tension of (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), γ_B(Dyne / cm) indicates the surface tension of the (B1) polyamide polymer in the (B) layered silicate-containing polyamide composition. )
[0011]
Further, the present invention comprises (A) a layer (a) composed of polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), and (B) a layered silicate-containing polyamide composition described above (B). b) layers and at least three layers of (c) layers comprising (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) or (C) polycaproamide (nylon 6) The present invention relates to a fuel tube characterized by the following.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The (A) polyundecaneamide (nylon 11) used in the present invention has the following formula having an acid amide bond (-CONH-): (-CO- (CH₂)₁₀-NH-)_nIs representative, and can be obtained by polymerizing 11-aminoundecanoic acid or undecanelactam. As polydodecaneamide (nylon 12), the following formula having an acid amide bond (-CONH-): (-CO- (CH₂)₁₁-NH-)_nIs representative, and can be obtained by polymerizing 12-aminododecanoic acid or dodecanelactam.
[0013]
The (C) polycaproamide (nylon 6) used in the present invention includes the following formula having an acid amide bond (—CONH—): (—CO— (CH₂)₅-NH-)_nIs a typical example, and can be obtained by polymerizing caprolactam or 6-aminocaproic acid.
[0014]
(A) Polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) and (C) polycaproamide (nylon 6) are copolymers containing the above monomer as a main component (60% by weight or more). It may be. Examples of the copolymer component include a lactam having three or more ring members, an aminocarboxylic acid, or a nylon salt comprising a diamine and a dicarboxylic acid.
[0015]
Examples of lactams having three or more rings include aminocarboxylic acids such as caprolactam (excluding nylon 6), enantholactam, undecane lactam (excluding nylon 11), dodecane lactam (excluding nylon 12), α-pyrrolidone, α-piperidone, and the like. Examples thereof include 6-aminocaproic acid (excluding nylon 6), 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid (excluding nylon 11), and 12-aminododecanoic acid (excluding nylon 12). Can be mentioned.
[0016]
Examples of the diamine constituting the nylon salt include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, , 9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1, 16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosandiamine, 2 / 3-methyl-1,5-pentanediamine, 2 -Methyl-1,8-octanediamine, 2,2,4 / 2,4,4- Aliphatic diamines such as 1,6-hexanediamine, 1,3 / 1,4-cyclohexanediamine, 1,3 / 1,4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) methane, bis (4- Aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, Alicyclic diamines such as 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornanedimethylamine and tricyclodecanedimethylamine, p-xylylenediamine And aromatics such as m-xylylenediamine Amine and the like can be mentioned.
[0017]
Examples of the dicarboxylic acids constituting the nylon salt include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandionic acid, dodecandionic acid, tridecandionic acid, tetradecandionic acid, pentadecandionic acid, hexadecandionic acid, Aliphatic dicarboxylic acids such as octadecanedioic acid and eicosandioic acid, alicyclic dicarboxylic acids such as 1,3 / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, and norbornanedicarboxylic acid; Aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, 1,4 / 2,6 / 2,7-naphthalenedicarboxylic acid and the like can be mentioned.
[0018]
Further, (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) and (C) polycaproamide (nylon 6) used in the present invention may be a homopolymer. However, it may be a mixture with the copolymer described above, or a mixture with another polyamide-based resin or another thermoplastic resin. The content of nylon 11 and / or nylon 12 and nylon 6 in the mixture is preferably 60% by weight or more.
[0019]
Other polyamide resins include polycaproamide (nylon 6) (excluding nylon 6), polyundecaneamide (nylon 11) (excluding nylon 11), polydodecaneamide (excluding nylon 12), polyethylene adipamide (Nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene azepamide (nylon 69), polyhexamethylene sebacamide (nylon 610), poly Hexamethylene undecamide (nylon 611), polyhexamethylene dodecamide (nylon 612), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene dodecamide (nylon 912), Polinona Tylene terephthalamide (nylon 9T), polydecamethylene dodecamide (nylon 1012), polydecamethylene terephthalamide (nylon 10T), polyundecamethylene terephthalamide (nylon 11T), polydodecamethylene dodecamide (nylon 1212) ), Polydodecamethylene terephthalamide (nylon 12T), polymethaxylylene adipamide (nylon MXD6), polytrimethylhexamethylene terephthalamide (TMHT), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), Examples include polybis (3-methyl-4-aminocyclohexyl) methandodecamide (nylon dimethyl PACM12) and copolymers using several kinds of these polyamide starting monomers.
[0020]
Other thermoplastic resins include high-density polyethylene (HDPE), low-density polyethylene (LDPE), ultra-high-molecular-weight polyethylene (UHMWPE), polypropylene (PP), ethylene-propylene copolymer (EPR), ethylene-butene A polyolefin-based resin such as a copolymer (EBR), and the above-mentioned polyolefin containing a carboxyl group and a functional group such as a metal salt thereof (Na, Zn, K, Ca, Mg), an acid anhydride group and an epoxy group; Resin, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN) , Polyester such as liquid crystal polyester Resin, polyacetal (POM), polyether resin such as polyphenylene oxide (PPO), polysulfone (PSF), polysulfone resin such as polyethersulfone (PES), polyphenylene sulfide (PPS), polythioether sulfone (PTES) ), Polyketone resins such as polyetheretherketone (PEEK) and polyallyletherketone (PEAK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), Polynitrile resins such as methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer (MBS), and polymethacrylate (PMMA), polymethacrylate resins such as polyethyl methacrylate (PEMA), ethylene / vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), Polyvinyl resins such as vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, cellulose resins such as cellulose acetate and cellulose butyrate, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and polychloride Fluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), Fluorinated resins such as trafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoroethylene / fluoro (alkyl vinyl ether) copolymer (PFA), thermoplastic polyimide (PI) ), Polyamide-imide (PAI), polyetherimide (PEI) and other polyimide-based resins, thermoplastic polyurethane-based resins, and the like.
[0021]
Further, a plasticizer may be added to (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) and (C) polycaproamide (nylon 6) used in the present invention. preferable. Examples of the plasticizer include benzenesulfonic acid alkylamides, toluenesulfonic acid alkylamides, and hydroxybenzoic acid alkyl esters.
[0022]
Examples of benzenesulfonic acid alkylamides include benzenesulfonic acid propylamide, benzenesulfonic acid butylamide, and benzenesulfonic acid 2-ethylhexylamide.
Examples of the toluenesulfonic acid alkylamides include N-ethyl-o- or N-ethyl-p-toluenesulfonic acid butylamide, N-ethyl-o- or N-ethyl-p-toluenesulfonic acid 2-ethylhexylamide, and the like. Is mentioned.
Examples of alkyl hydroxybenzoates include ethylhexyl o- or p-hydroxybenzoate, hexyldecyl o- or p-hydroxybenzoate, ethyldecyl o- or p-hydroxybenzoate, octyloctyl o- or p-hydroxybenzoate. Decyldodecyl o- or p-hydroxybenzoate, methyl o- or p-hydroxybenzoate, butyl o- or p-hydroxybenzoate, hexyl o- or p-hydroxybenzoate, o- or p-hydroxybenzoic acid n-octyl, decyl o- or p-hydroxybenzoate and dodecyl o- or p-hydroxybenzoate.
[0023]
Among them, benzenesulfonic acid alkylamides such as benzenesulfonic acid butylamide and benzenesulfonic acid 2-ethylhexylamide, and N-ethyl-p-toluenesulfonic acid butylamide and N-ethyl-p-toluenesulfonic acid 2-ethylhexylamide. Toluenesulfonic acid alkylamides and hydroxybenzoic acid alkyl esters such as ethylhexyl p-hydroxybenzoate, hexyldecyl p-hydroxybenzoate and ethyldecyl p-hydroxybenzoate are preferably used. Particularly preferably, butyl sulfonic acid butylamide, ethylhexyl p-hydroxybenzoate, hexyldecyl p-hydroxybenzoate and the like are used.
[0024]
The amount of the plasticizer is 1 to 30 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the polyamide resin component. If the amount of the plasticizer exceeds 30 parts by weight, the low-temperature impact resistance of the fuel tube is undesirably reduced.
[0025]
An impact modifier may be added to (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) and (C) polycaproamide (nylon 6) used in the present invention. Is preferred. Examples of the impact modifier include a rubber-like polymer, and those having a tensile modulus of 500 MPa or less measured according to ASTM D882 are preferable. If the tensile modulus is higher than this value, it will be insufficient as an impact modifier.
[0026]
Examples of the impact modifier include (ethylene and / or propylene) · α-olefin copolymers, (ethylene and / or propylene) · (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymers. Examples thereof include polymers, ionomer polymers, and aromatic vinyl compound / conjugated diene compound-based block copolymers, and these can be used alone or in combination.
[0027]
The (ethylene and / or propylene) -α-olefin-based copolymer is a polymer obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms. As the α-olefin having 3 or more carbon atoms, Propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 4-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-e -1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof.
Also, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1, 5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8- Decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropyl-2-norbornene, 2,3-diisopropylidene- - norbornene, 2-ethylidene-3-isopropylidene-5-norbornene may be copolymerized non-conjugated diene polyene such as 2-propenyl-2,2-norbornadiene.
[0028]
The (ethylene and / or propylene) · (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) -based copolymer is defined as ethylene and α, β-unsaturated carboxylic acid α, β-unsaturated. It is a polymer obtained by copolymerizing a saturated carboxylic acid and / or unsaturated carboxylic acid ester monomer. Examples of the α, β-unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid. And β-unsaturated carboxylic acid ester monomers such as methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, nonyl ester, and decyl ester of these unsaturated carboxylic acids. Or a mixture thereof.
[0029]
The ionomer polymer is obtained by neutralizing at least a part of the carboxyl groups of the olefin and the α, β-unsaturated carboxylic acid copolymer by neutralizing metal ions. Ethylene is preferably used as the olefin, and acrylic acid and methacrylic acid are preferably used as the α, β-unsaturated carboxylic acid. The body may be copolymerized. Metal ions include alkali metals such as Li, Na, K, Mg, Ca, Sr, and Ba, and alkaline earth metals, Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu, Zn, and Cd. Can be mentioned.
[0030]
The aromatic vinyl compound / conjugated diene compound-based block copolymer is a block copolymer composed of an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block, and is an aromatic vinyl compound-based polymer. A block copolymer having at least one block and at least one conjugated diene-based polymer block is used. In the above block copolymer, unsaturated bonds in the conjugated diene-based polymer block may be hydrogenated.
[0031]
The aromatic vinyl compound-based polymer block is a polymer block mainly composed of structural units derived from an aromatic vinyl compound. As the aromatic vinyl compound in that case, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinyl Anthracene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and the like can be mentioned, and the aromatic vinyl compound-based polymer block is as described above. May have a structural unit composed of one or more of the above-mentioned monomers. In addition, the aromatic vinyl compound-based polymer block may have a structural unit composed of a small amount of another unsaturated monomer in some cases.
[0032]
Conjugated diene-based polymer blocks include 1,3-butadiene, chloroprene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene 1,6-hexadiene And the like. In a hydrogenated aromatic vinyl compound / conjugated diene block copolymer, an unsaturated bond in the conjugated diene-based polymer block is a polymer block formed from one or more conjugated diene-based compounds. Part or all of the part is in a saturated bond by hydrogenation. Here, the distribution in the polymer block mainly composed of a conjugated diene may be random, tapered, partially block-shaped, or an arbitrary combination thereof.
[0033]
The molecular structure of the aromatic vinyl compound / conjugated diene block copolymer and its hydrogenated product may be any of linear, branched, radial, or any combination thereof. Among them, in the present invention, one aromatic vinyl compound polymer block and one conjugated diene polymer block are linearly formed as an aromatic vinyl compound / conjugated diene block copolymer and / or a hydrogenated product thereof. A diblock copolymer, an aromatic vinyl compound polymer block, a conjugated diene polymer block, and a triblock copolymer in which three polymer blocks are linearly bonded in this order. And one or more of these hydrogenated products are preferably used. Unhydrogenated or hydrogenated styrene / butadiene copolymer, unhydrogenated or hydrogenated styrene / isoprene copolymer, unhydrogenated or hydrogenated Styrene / isoprene / styrene copolymer, unhydrogenated or hydrogenated styrene / butadiene / styrene copolymer, unhydrogenated or hydrogenated styrene / (isoprene / butyl Diene) / styrene copolymer, and the like.
[0034]
(Ethylene and / or propylene) α-olefin-based copolymer, (ethylene and / or propylene) (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) used as impact modifier As the system copolymer, the ionomer polymer, and the block copolymer of the aromatic vinyl compound and the conjugated diene compound, a polymer modified with a carboxylic acid and / or a derivative thereof is preferably used. By modifying with such a component, a functional group having an affinity for the polyamide resin is included in the molecule.
[0035]
Examples of the functional group having affinity for the polyamide resin include a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal base, a carboxylic acid imide group, a carboxylic acid amide group, and an epoxy group. . Examples of compounds containing these functional groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methyl maleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid, and cis-4-acid. Cyclohexene-1,2-dicarboxylic acid, endobicyclo- [2,2,1] -5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, methyl acrylate, Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride , Itaconic anhydride, Water citraconic acid, endobicyclo- [2,2,1] -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, Glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid and the like can be mentioned.
[0036]
The compounding amount of the impact modifier is 1 to 35 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the polyamide resin component. If the amount of the impact modifier exceeds 35 parts by weight, the original mechanical properties of the fuel tube are impaired, which is not preferable.
[0037]
In the fuel tube according to the present invention, (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), and (C) polycaproamide (nylon 6) are blended with a conductive filler. be able to. Conductivity means that, for example, when a flammable fluid such as gasoline continuously contacts an insulator such as a resin, static electricity may accumulate and ignite. It has electrical characteristics. There is no problem if any of the layers using the resin composition imparted with conductivity is arranged in any layer, but is preferably arranged in the innermost layer. This makes it possible to prevent explosion due to static electricity generated when a fluid such as fuel is transported.
[0038]
The conductive filler referred to in the present invention includes all fillers added for imparting a conductive property to a resin, and includes granular, flake-like and fibrous fillers.
[0039]
As the granular filler, carbon black, graphite and the like can be suitably used. As the flake filler, aluminum flake, nickel flake, nickel-coated mica and the like can be suitably used. As the fibrous filler, carbon fibers, carbon-coated ceramic fibers, carbon whiskers, metal fibers such as aluminum fibers, copper fibers, brass fibers, and stainless fibers can be suitably used. Of these, carbon black is most preferred.
[0040]
The carbon black that can be used in the present invention includes all carbon blacks generally used for imparting conductivity. Preferred carbon blacks include acetylene black obtained by completely burning acetylene gas and ketjen black oil black, naphthalene black, and thermal black produced by furnace type incomplete combustion using crude oil as lamp black, channel black, Examples thereof include roll black and disk black, but are not limited thereto. Acetylene black and furnace black (Ketjen black) are particularly preferably used.
[0041]
As for carbon black, various carbon powders having different properties such as particle diameter, surface area, DBP oil absorption, and ash content are produced. The carbon black that can be used in the present invention is not particularly limited in these characteristics, but preferably has a good chain structure and a large aggregation density. A large amount of carbon black is not preferable in terms of impact resistance. From the viewpoint of obtaining excellent electrical conductivity with a smaller amount, the average particle size is preferably 500 nm or less, particularly 5 to 100 nm, more preferably 10 to 70 nm. (BET method) is 10m²/ G or more, and 300m²/ G or more, especially 500 to 1500 m²/ G is preferred, and the DBP (dibutyl phthalate) oil absorption is preferably 50 ml / 100 g or more, particularly preferably 100 ml / 100 g, and more preferably 300 ml / 100 g or more. The ash content is preferably 0.5% or less, particularly preferably 0.3% or less. The DBP oil absorption here is a value measured by a method defined in ASTM-D2414. The carbon black more preferably has a volatile content of less than 1.0% by weight.
[0042]
These conductive fillers may be subjected to a surface treatment with a surface treatment agent such as a titanate, aluminum, or silane. It is also possible to use a granulated material for improving the workability of melt-kneading.
[0043]
The amount of the conductive filler is different depending on the type of the conductive filler to be used, and therefore cannot be specified unconditionally, but from the viewpoint of the balance between conductivity and fluidity, mechanical strength, etc., based on 100 parts by weight of the polyamide resin component. Generally, 3 to 30 parts by weight is preferably selected.
Further, such a conductive filler has a surface specific resistance of 10%, which is obtained by melt-extruding a polyamide resin composition containing the conductive filler, in order to obtain sufficient antistatic performance.⁸  Ω / square or less, especially 10⁶It is preferable that it be Ω / square or less. However, the compounding of the conductive filler tends to cause deterioration in strength and fluidity. Therefore, if the target conductivity level is obtained, it is desirable that the amount of the conductive filler is as small as possible.
[0044]
Furthermore, if necessary, (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) and (C) polycaproamide (nylon 6) used in the present invention may have antioxidation. An agent, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant, a crystallization accelerator and the like may be added.
[0045]
(A) Polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) and (C) polycaproamide (nylon 6) are known polymerization methods for polyamide, such as melt polymerization, solution polymerization and solid phase polymerization. Can be done with As the production apparatus, known polyamides such as kneading reaction extruders such as batch reactors, single-tank or multi-tank continuous reactors, tubular continuous reactors, single-screw kneading extruders, and twin-screw kneading extruders can be used. Manufacturing equipment can be used. As a polymerization method, known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be used, and normal pressure, reduced pressure, and pressurized operations can be repeated for polymerization. These polymerization methods can be used alone or in an appropriate combination.
[0046]
Further, (A) polyundecaneamide (nylon 11) and / or polydodecanamide (nylon 12) have a relative viscosity of 1.5 to 4.0, preferably 2 in accordance with JIS K-6920. 0.0 to 3.5. Further, (C) polycaproamide (nylon 6) has a relative viscosity of 2.0 to 5.0, preferably 2.5 to 4.5, measured according to JIS K-6920. When the relative viscosity of (A) polyundecaneamide (nylon 11) and / or polydodecanamide (nylon 12) and (C) polycaproamide (nylon 6) is smaller than the above value, mechanical properties of the resulting fuel tube are reduced. In some cases, the properties are insufficient, and when the value is larger than the above-mentioned values, the extrusion pressure and the torque may be too high, and it may be difficult to manufacture the fuel tube.
[0047]
The (B) layered silicate-containing polyamide composition used in the present invention has an acid amide bond (—CONH—) in a molecular chain, and has a lactam, an amino acid, or a diamine having three or more membered rings. A nylon salt composed of dicarboxylic acid is used as a polyamide raw material monomer and comprises a polyamide polymer (B1) satisfying the following formula (1) and a layered silicate (B2) uniformly dispersed in the molecule.
[0048]
3.0 ≦ γ_B  −γ_A  ≦ 10.0 (1)
(Where γ_A(Dyne / cm) is the surface tension of (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), γ_B(Dyne / cm) indicates the surface tension of the (B1) polyamide polymer in the (B) layered silicate-containing polyamide composition. )
[0049]
The surface tension difference (Δγ) of (A) and (B) needs to be 3.0 or more and 10.0 or less, and preferably 3.5 or more and 9.5 or less. When the surface tension difference (Δγ) is larger than 10.0, the (A) layer composed of (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), and the (B) layered silicate It becomes impossible to obtain sufficient interlayer adhesion with the layer (b) made of the containing polyamide composition. When the surface tension difference (Δγ) is smaller than 3.0, the interlayer adhesion is inferior as described above, and alcohol gasoline is prevented from permeating even in a fuel tube using the (B) layered silicate-containing polyamide composition. May be inferior.
[0050]
The surface tension (γ) used in the present invention is a calculated value based on only the chemical structure of a substance obtained by the following equation. [Wherein, ΔEi is the contribution to the molar cohesion energy due to the interaction of each atom with each atom (J / mol), and ΔVi is the increment of the van der Waals volume (ų  ) And A represent the number of atoms in the repeating unit. ]
[0051]
(Equation 1)

[0052]
(A) Polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) have a surface tension of 34.9 and 33.8 (dyne / cm), respectively. In order to satisfy the above condition of the surface tension, the surface tension of the (B1) polyamide polymer in the (B) layered silicate-containing polyamide composition is, for example, 36 when polydodecaneamide (nylon 12) is used. .8 ≦ γ_B  ≤43.8. Therefore, in order to satisfy the condition of the surface tension, the polyamide raw material monomer forming the polyamide polymer (B1) in the (B) layered silicate-containing polyamide composition is mixed with a lactam, amino acid, or diamine having three or more ring members. It is appropriately determined from nylon salts composed of dicarboxylic acid and the like.
[0053]
In order to satisfy the above condition of surface tension, a polyamide polymer containing at least one or more kinds of repeating structural units selected from the group consisting of caproamide, dodecaneamide, hexamethylene dodecamide, and dodecamethylene adipamide may be mentioned. it can. Specifically, hexamethylene dodecamide polymer (nylon 612), dodecamethylene adipamide polymer (nylon 126), caproamide / dodecaneamide copolymer (nylon 6/12 copolymer), caproamide / hexamethylene dodeca Amide polymer (nylon 6/612 copolymer), caproamide / dodecamethylene adipamide polymer (nylon 6/126 copolymer), caproamide / dodecanamide / hexamethylene dodecamide copolymer (nylon 6/12 / 612 copolymer).
[0054]
Among them, a caproamide / dodecaneamide copolymer (nylon 6/12 copolymer) and / or a hexamethylene dodecamide polymer (nylon 612) are more preferable. In the case where the polyamide polymer (B1) is a copolymer, the composition ratio of caproamide and dodecaneamide units can be appropriately determined so as to satisfy the above-mentioned surface tension condition. Furthermore, a mixture of caproamide / dodecaneamide copolymer (nylon 6/12 copolymer) having different composition ratios of caproamide and dodecaneamide unit may be used as long as the above conditions of the surface tension are satisfied.
[0055]
In the present invention, the (B2) layered silicate contained in the (B) layered silicate-containing polyamide composition is uniformly dispersed at the molecular level without local aggregation, forming a silicate layer. There is a need. Here, the silicate layer is a basic unit constituting the (B2) layered silicate, and is obtained by cleaving the (B2) layered silicate. Here, the (B2) layered silicate preferably represents, for example, one unit of a substance having a size of 0.002 to 1 μm and a thickness of 6 to 20 °.
[0056]
The term "uniformly dispersed at the molecular level" as used herein means a state in which when the (B2) layered silicate is dispersed in the (B1) polyamide polymer, each of them maintains an interlayer distance of 20 ° or more on average. . Here, the interlayer distance refers to the distance between the centers of gravity of the (B2) layered silicate plates, and the dispersed state means that each (B2) layered silicate has an average overlap of 5 layers or less. This refers to a state in which 50% by weight or more, preferably 70% by weight or more of the laminates are dispersed without forming a lump in a state of being parallel or randomly, or a mixture of parallel and random. Specifically, (B) wide-angle X-ray diffraction measurement was performed on a test piece of the layered silicate-containing polyamide composition, and it was confirmed that the peak due to the thickness direction of the silicate layer had disappeared, or a transmission electron micrograph. By photographing observation, it can be confirmed from the absence of a layered silicate mass.
[0057]
Preferred examples of the layered silicate (B2) used in the present invention include smectites such as montmorillonite, beidellite, saponite, hectorite, and sauconite, vermiculites such as vermiculite, fluoromica, muscovite, paragonite, phlogopite, black mica. Examples include mica, lepidolite and other mica, brittle mica such as margarite, clintnite, and anandite, and chlorite such as dombasite, sodoite, couquaite, clinochlore, chamosite, and nimite.
The (B2) layered silicate exemplified above may be natural, synthetic or modified, and may be used alone or in combination of several kinds.
[0058]
(B2) The layered silicate has a structure composed of a negatively charged layer containing silicate as a main component and a positive charge (ion) having an ion exchange capability interposed between the layers.
[0059]
It is desirable that the cation exchange capacity (CEC) of these (B2) layered silicates is in the range of 50 to 200 meq / 100 g. The cation exchange capacity is measured by measuring the amount of adsorbed methylene blue. When the cation exchange capacity is less than 50 meq / 100 g, the dispersion cleavage of the (B2) layered silicate may not proceed sufficiently. On the other hand, if the cation exchange capacity exceeds 200 meq / 100 g, the bonding strength between the layers is so strong that cleavage of the (B2) layered silicate may be difficult.
[0060]
In particular, montmorillonite obtained by purifying bentonite is most suitable for the present invention because of its cation exchange capacity and availability.
[0061]
Montmorillonite is represented by the following formula and can be obtained by purifying naturally occurring products. M_a  Si₄  (Al_2-a  Mg_a  ) O₁₀(OH)₂  ・ NH₂  O (where M represents a cation of sodium, a is 0.25 to 0.60. The number of water molecules bonded to the ion-exchangeable cation between the layers is determined by the cation species, humidity, etc. (Hereinafter, it is represented by nH2O in the formula since it can vary depending on conditions.)
Montmorillonite also includes the same type ion substitutes of magnesia montmorillonite, iron montmorillonite, and iron magnesia montmorillonite represented by the following formula group, and these may be used.
M_a  Si₄  (Al_{1 . 67-a}Mg_{0 . 5 + a}  ) O₁₀(OH)₂  ・ NH₂  O
M_a  Si₄  (Fe_2-a  ^{3 +}Mg_a) O₁₀(OH)₂  ・ NH₂  O
M_a  Si₄  (Fe_{1 . 67-a} ^{3 +}Mg_{0 . 5 + a}  ) O₁₀(OH)₂  ・ NH₂O
(In the formula, M represents a cation of sodium, and a is 0.25 to 0.60.)
[0062]
Normally, montmorillonite has ion-exchangeable cations such as sodium and calcium between its layers, but the content ratio varies depending on the place of production. In the present invention, it is necessary that the ion-exchangeable cation between the layers is replaced with sodium by an ion-exchange treatment or the like. It is preferable to use montmorillonite purified by water treatment.
[0063]
In the present invention, for the purpose of further improving dispersibility, a layered silicate in which an organic onium ion is inserted (intercalated) between the layers of the layered silicate (B2) is preferably used.
[0064]
The organic onium ion has a structure represented by an ammonium ion, a phosphonium ion, a sulfonium ion, an onium ion derived from a heteroaromatic ring, or the like. Among these, from the viewpoints of availability and stability, ammonium ions, phosphonium ions, and onium ions derived from a heteroaromatic ring are preferred.
[0065]
Examples of the ammonium ion include alkyl ammonium such as hexyl ammonium, octyl ammonium, decyl ammonium, dodecyl ammonium, hexadecyl ammonium, and octadecyl ammonium; ammonium of a primary amine having a hydroxyl group such as ethanolamine, p-aminophenol, and m-aminophenol. Α-amino acids such as glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, threonine, serine, proline, tryptophan, thyroxine, methionine, cystine, cysteine, asparagine, aspartic acid, glutamine, glutamic acid, lysine, arginine and histidine. Ammonium, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononane Primary ammoniums such as ammonium of ω-amino fatty acids such as 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, dialkylammoniums such as methyldodecylammonium, butyldodecylammonium and methyloctadecylammonium, diethanolamine and the like Secondary ammoniums such as ammonium secondary amine having a hydroxyl group, trialkyl ammonium such as dimethyloctyl ammonium, dimethyl dodecyl ammonium, dimethyl hexadecyl ammonium, dimethyl octadecyl ammonium, dimethyl phenyl ammonium, diphenyl dodecyl ammonium, diphenyl octadecyl ammonium, etc. Tertiary ammonium having a hydroxyl group such as tertiary ammonium having a phenyl group and triethanolamine Quaternary ammonium having the same alkyl group such as tetraethylammonium, tetrabutylammonium, tetraoctylammonium, trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexa Decyl ammonium, trimethyl octadecyl ammonium, trimethyl eicosanyl ammonium, trimethyl octadecenyl ammonium, trimethyl octadecenyl ammonium, etc., trimethyl alkyl ammonium, triethyl dodecyl ammonium, triethyl tetradecyl ammonium, triethyl hexadecyl ammonium, triethyl octadecyl ammonium, etc. Triet Alkyl ammonium, tributyl dodecyl ammonium, tributyl tetradecyl ammonium, tributyl hexadecyl ammonium, tributyl alkyl ammonium such as tributyl octadecyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl didodecyl ammonium, dimethyl ditetradecyl ammonium, dimethyl dihexadecyl Ammonium, dimethyldioctadecylammonium, dimethyldioctadecenylammonium, dimethyldialkylammonium such as dimethyldioctadecadienylammonium, diethyldidodecylammonium, diethylditetradecylammonium, diethyldihexadecylammonium, diethyldioctadecylammonium, etc. Of diethyldia Dibutyldialkylammonium such as alkylammonium, dibutyldidodecylammonium, dibutylditetradecylammonium, dibutyldihexadecylammonium, dibutyldioctadecylammonium; methylbenzyldialkylammonium such as methylbenzyldihexadecylammonium; dibenzyldihexadecylammonium Trialkylmethylammonium, such as dibenzyldialkylammonium, trioctylmethylammonium, tridodecylmethylammonium and tritetradecylmethylammonium; trialkylethylammonium such as trioctylethylammonium and tridodecylethylammonium; trioctylbutylammonium; Trialkylbutyl such as dodecylbutylammonium Ammonium, quaternary ammonium having an aromatic ring such as trimethyl benzyl ammonium, ions such as quaternary ammonium derived from an aromatic amine such as trimethylphenyl ammonium.
[0066]
Examples of the phosphonium ion include quaternary phosphonium such as tetrabutylphosphonium, tetraoctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributyldodecylphosphonium, tributylhexadecylphosphonium, and tributyloctadecylphosphonium; Quaternary phosphoniums such as phenylalkyl quaternary phosphoniums such as trimethylphosphonium, phenyltributylphosphonium, diphenyldimethylphosphonium, triphenylmethylphosphonium, and tetraphenylphosphonium; as onium ions derived from a heteroaromatic ring, pyridinium, methylpyridinium, dimethyl Pyridinium, mushroom Um, and ion such as isoquinolinium. The above may be an ammonium ion or a phosphonium ion to which ethylene oxide is added to impart hydrophilicity. These may be used in combination of plural kinds.
[0067]
Among these organic onium ions, those having a relatively low molecular weight, for example, alkyl ammonium such as hexyl ammonium, octyl ammonium, and decyl ammonium, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, and 9-aminononanoic acid Ammonium, valine, leucine, isoleucine, phenylalanine, tyrosine, threonine, serine, proline, hydroxyproline, tryptophan, ω-aminoaliphatic carboxylic acid such as 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid; Primary ammoniums such as ammonium of α-amino acids such as methionine, cystine, cysteine, aspartic acid, glutamic acid, asparagine, glutamine, lysine, arginine and histidine; pyridinium; Oniums derived from a heteroaromatic ring such as tylpyridinium and dimethylpyridinium are preferred, and more preferably 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Ammonium ions of ω-aminoaliphatic carboxylic acids such as ammonium and pyridinium, most preferably ammonium ions of ω-aminoaliphatic carboxylic acids such as 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are used. You.
[0068]
The amount of the organic onium ion is not particularly limited as long as it is in the range of 0.8 to 2.0 equivalents to the cation exchange capacity of the layered silicate (B2), but is usually about 0.9 to 1.3 equivalents. Become. When the amount is less than 0.8 equivalent, the dispersibility in the polyamide resin decreases, and when the amount is more than 2.0 equivalents, the free compound derived from the onium ion becomes remarkable, the thermal stability decreases during molding, It may cause emission, smoking, mold contamination, odor, etc.
[0069]
The insertion of the organic onium ion between the layers of the (B2) layered silicate is facilitated by adding the onium ion or a solution containing the same to the suspension of the (B2) layered silicate and performing cation exchange. Is achieved. By introducing the onium ion between the layers, which is simply performed by contacting the (B2) layered silicate with the organic onium ion in the solvent-containing solvent, an organic structure can be introduced between the layers of the negatively charged silicate layer. As a result, penetration of the polyamide raw material between layers and progress of polymerization are promoted, and uniform dispersion of the (B2) layered silicate in the (B1) polyamide polymer is achieved.
[0070]
The dispersion medium used when inserting the organic onium ion between the layers of the (B2) layered silicate can be appropriately determined depending on the type of the (B2) layered silicate, the organic onium ion and the (B1) polyamide polymer. Preferably, the layered silicate is uniformly dispersed and has good compatibility with the swelling agent and the polyamide polymer.
[0071]
As the dispersion medium, water, methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, 1,4-butanediol, glycerin, dimethyl sulfoxide, dimethylformamide, acetic acid, formic acid, pyridine, aniline, phenol, nitrobenzene, acetonitrile, acetone , Methyl ethyl ketone, chloroform, carbon disulfide, propylene carbonate, 2-methoxyethanol, ether, carbon tetrachloride, n-hexane, caprolactam, dodecane lactam, 6-aminocaproic acid, 12-aminododecanoic acid, and the like. One or more kinds of dispersion media can be used. In particular, it is preferable to use water, methanol, ethanol and / or caprolactam as the dispersion medium.
[0072]
The amount of the layered silicate (B2) in the present invention is preferably 0.1 to 30% by weight, more preferably 0.5 to 10% by weight. (B2) When the addition amount of the layered silicate is less than 0.1% by weight, the alcohol gasoline permeation-preventing property is not sufficient, and when it is more than 30% by weight, (B) the layered silicate polyamide composition in the fuel tube Even if the material layer is made thin, tube forming becomes difficult, and low-temperature impact resistance and tensile elongation decrease, which is not preferable.
[0073]
(B1) The method of uniformly dispersing the (B2) layered silicate in the polyamide polymer is as follows: (1) The (B2) layered silicate is brought into contact with a swelling agent, and the interlayer is expanded in advance to take in monomer molecules between the layers. (B2) The layered silicate swells in the dispersion medium by mixing (B1) a polyamide raw material monomer of a polyamide polymer with a polyamide raw material monomer and polymerizing (see JP-A-62-74957). A method of mixing or kneading the layered silicate composite uniformly dispersed in the state with the polyamide polymer (B1) (see JP-A-2-305828), and (3) containing a high concentration of the layered silicate (B2). ) The layered silicate-containing polyamide composition is prepared in advance by the above-mentioned method, and the method of (B2) mixing the layered silicate-containing polyamide composition and the layered silicate-free (B1) polyamide polymer is applied. Can.
[0074]
The (B) layered silicate-containing polyamide composition used in the present invention has a relative viscosity of 1.5 to 6.0, preferably 2.0 to 5.0, more preferably 2.0 to 5.0 as measured according to JIS K6920. 2.0 to 4.5. When the relative viscosity is less than 1.5, the mechanical properties of the obtained fuel tube are reduced. On the other hand, when it is larger than 6.0, the viscosity at the time of melting becomes high, and it becomes difficult to form a tube.
[0075]
The (B) layered silicate-containing polyamide composition used in the present invention may optionally contain an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, inorganic fine particles, an antistatic agent, Agents, flame retardants, crystallization accelerators, glass fibers, plasticizers, impact modifiers, conductive fillers and the like.
[0076]
The fuel tube according to the present invention comprises (A) a layer (a) made of polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), and (B1) a polyamide satisfying the following formula (1). Consisting of at least two layers, including (B2) a layer composed of a (B2) layered silicate-containing polyamide composition in which 0.1 to 30% by weight of (B2) a layered silicate is uniformly dispersed in the polymer. Is done.
[0077]
3.0 ≦ γ_B  −γ_A  ≦ 10.0 (1)
(Where γ_A(Dyne / cm) is the surface tension of (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), γ_B(Dyne / cm) indicates the surface tension of the (B1) polyamide polymer in the (B) layered silicate-containing polyamide composition. )
[0078]
In the present invention, (A) a layer (a) composed of polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), and (B1) a polyamide polymer satisfying the above-mentioned formula (1) and its polyamide polymer By using the (B) layer composed of the (B) layered silicate-containing polyamide composition in which 0.1 to 30% by weight of the (B2) layered silicate is uniformly dispersed in the molecule, the (a) layer and the (b) ) Layers can be laminated directly without the use of an adhesive layer, so that cost and management complexity due to an increase in the number of layers can be suppressed, and alcohol gasoline penetration prevention, interlayer adhesion, and low temperature impact resistance A fuel tube having excellent properties can be obtained.
[0079]
As a preferred embodiment, (A) a layer composed of polyundecaneamide (nylon 11) and / or polydodecanamide (nylon 12), and (B) a layered silicate-containing polyamide composition described above (B) b) and at least three layers, including (A) polyundecaneamide (nylon 11) and / or polydodecanamide (nylon 12) or (C) a layer of polycaproamide (nylon 6). Be composed.
[0080]
In the fuel tube of the present invention, the (a) layer made of (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) is preferably arranged as the outermost layer of the fuel tube. (A) If the layer composed of polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) is not disposed as the outermost layer, the resin may be deteriorated by the road deicing agent.
[0081]
Further, in the fuel tube of the present invention, the (c) layer made of (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) or (C) polycaproamide (nylon 6) has a fuel layer. When arranged in the innermost layer of the fuel tube, it is possible to obtain a fuel tube which is excellent in chemical resistance and impact resistance and is economically advantageous. Further, in order to prevent the spark generated by the internal friction of the fuel circulating in the pipe or the friction with the pipe wall from igniting the fuel, (A) polyundecanamide (nylon 11) and / or It is preferable that a layer made of dodecaneamide (nylon 12) or (C) polycaproamide (nylon 6) is disposed as the innermost layer. At this time, a layer made of (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) or (C) polycaproamide (nylon 6), which does not have conductivity, is formed on the conductive layer. By arranging it on the outer layer side, it is possible to achieve both low-temperature impact resistance and conductivity, and it is economically advantageous.
[0082]
In the fuel tube of the present invention, it is essential to include the layer (B) composed of the layered silicate-containing polyamide composition (B), and it is more preferable that the layer is disposed in the intermediate layer of the fuel tube. If the (B) layer composed of the (B) layered silicate-containing polyamide composition is not disposed, the fuel tube will have a poor ability to prevent alcohol gasoline from permeating.
[0083]
In the fuel tube of the present invention, the thickness of each layer is not particularly limited, and can be adjusted according to the type of polymer constituting each layer, the total number of layers in the fuel tube, the application, and the like. The thickness of each layer is determined in consideration of the properties of the fuel tube, such as alcohol gasoline permeation prevention properties, low-temperature impact resistance, and flexibility. Generally, the layers (a), (b), and (c) The thickness of each layer is preferably 3 to 90% with respect to the thickness of the entire fuel tube. In consideration of the alcohol gasoline permeation prevention property, the thickness of the layer (b) is more preferably 5 to 80%, and still more preferably 10 to 50%, based on the thickness of the entire fuel tube.
[0084]
The total number of layers in the fuel tube of the present invention is not particularly limited, and (A) a layer composed of (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), and (B) a layered structure. (A) a layer comprising at least two layers (b) composed of a silicate-containing polyamide composition, preferably (A) a layer composed of polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12); B) a layer (b) comprising a layered silicate-containing polyamide composition, and (A) polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12) or (C) polycaproamide (nylon 6) Any layer may be used as long as it has at least three layers, including the layer (c). Further, the fuel tube of the present invention may have one layer or two or more layers made of another thermoplastic resin in addition to the three layers (a), (b) and (c). Good.
[0085]
Other thermoplastic resins include polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), polyethylene Polyester resins such as naphthalate (PEN) and liquid crystal polyester (LCP); polyether resins such as polyacetal (POM) and polyphenylene oxide (PPO); polysulfone resins such as polysulfone (PSF) and polyether sulfone (PES) , Polythioether resins such as polyphenylene sulfide (PPS) and polythioether sulfone (PTES), and polyketone trees such as polyether ether ketone (PEEK) and polyallyl ether ketone (PEAK) , Polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), methacrylonitrile / styrene / butadiene Polynitrile resins such as copolymer (MBS), polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), polyvinyl acetate resins such as polyvinyl acetate (PVAc), and polychlorinated resin Polyvinyl chloride resins such as vinylidene (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer; cellulose resins such as cellulose acetate and cellulose butyrate; Vinylide (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexa Fluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoroethylene / fluoro (alkyl vinyl ether) copolymer ( PFA), polycarbonate resin such as polycarbonate (PC), polyimide resin such as thermoplastic polyimide (PI), polyamide imide (PAI), polyether imide (PEI), thermoplastic resin Urethane resin, polyethylene adipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene azepamide (nylon 69), polyhexamethylene se Bacamide (nylon 610), polyhexamethylene undecamide (nylon 611), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene dodecamide (nylon 912), polynona Methylene terephthalamide (nylon 9T), polydecamethylene dodecamide (nylon 1012), polydecamethylene terephthalamide (nylon 10T), polyundecamethylene terephthalamide (nylon 11T), polydodecamethylene dodeca (Nylon 1212), polydodecamethylene terephthalamide (nylon 12T), polymethaxylylene adipamide (nylon MXD6), polytrimethylhexamethylene terephthalamide (TMHT), polybis (4-aminocyclohexyl) methane dodecamide ( Examples thereof include polyamide resins such as nylon PACM12), polybis (3-methyl-4-aminocyclohexyl) methandodecamide (nylon dimethyl PACM12), and copolymers using several kinds of polyamide raw material monomers forming these. Among them, polyester resins, polyamide resins, polythioether resins, and fluorine resins are preferably used.
[0086]
It is also possible to laminate any substrate other than the thermoplastic resin, for example, paper, metal-based material, non-stretched, uniaxially or biaxially stretched plastic film or sheet, woven fabric, nonwoven fabric, metal flocculent, woody, etc. It is. Metal-based materials include metals and metal compounds such as aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, and cobalt, and two or more of these. Examples include alloy steels such as stainless steel, aluminum alloys, copper alloys such as brass and bronze, and alloys such as nickel alloys.
[0087]
The number of layers of the fuel tube of the present invention is 2 or more, and is 8 or less, preferably 3 to 7 layers, more preferably 3 to 6 layers as judged from the mechanism of the tube manufacturing apparatus.
[0088]
The outer diameter of the fuel tube of the present invention is determined in consideration of the flow rate of the fuel (for example, gasoline), and the thickness is such that the permeability of the fuel does not increase and that the normal tube burst pressure can be maintained. The thickness is designed to be such that the tube can be easily assembled and the vibration resistance during use can maintain a good degree of flexibility, and is not limited. Preferably, the outer diameter is 4 to 30 mm, the inner diameter is 3 to 25 mm, and the wall thickness is 0.05 to 5 mm.
[0089]
As a method for producing the fuel tube of the present invention, a method of melting and extruding using an extruder corresponding to the number of layers or the number of materials, and simultaneously laminating inside or outside the die (co-extrusion method), or A method (coating method) in which a single-layer tube or a laminated tube manufactured by the above-described method is manufactured in advance, and a resin is integrated to the outside, and an adhesive is used, if necessary, to integrate and laminate the resin. Can be mentioned.
[0090]
Further, when the fuel tube of the present invention has a complicated shape, or when subjected to heating and bending after molding to form a molded product, the above-described fuel tube is used to remove residual distortion of the molded product. After the formation, it is also possible to obtain a desired molded product by performing a heat treatment at a temperature lower than the lowest melting point of the resin constituting the tube for 0.01 to 10 hours.
[0091]
The fuel tube of the present invention may have a corrugated region in the middle thereof. Such a corrugated region is a region in which an appropriate region in the middle of the tube body is formed into a corrugated shape, a bellows shape, an accordion shape, a corrugated shape, or the like.
By having a region in which a plurality of such wavy folds are arranged in a ring shape, one side of the ring can be compressed and the other side can be stretched outward in that region, so that stress fatigue and delamination between layers can be achieved. It is possible to easily bend at an arbitrary angle without accompanying.
[0092]
The corrugated region of the fuel tube of the present invention can be easily formed by first molding a straight tubular tube and then molding it to form a predetermined corrugated shape. The fuel tube of the present invention may not only have a corrugated region over its entire length, but may have a corrugated region partially.
[0093]
The whole or a part of the outer periphery of the fuel tube thus formed may be made of epichlorohydrin rubber, NBR, a mixture of NBR and polyvinyl chloride, chlorosulfonated polyethylene in consideration of stone splash, abrasion with other parts and flame resistance. Rubber, chlorinated polyethylene rubber, acrylic rubber (ACM), chloroprene rubber (CR), ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), rubber mixture of NBR and EPDM, vinyl chloride, olefin, A solid or sponge-like protective member (protector) made of an ester-based, amide-based thermoplastic elastomer or the like can be provided. The protection member may be a sponge-like porous body by a known method. By using a porous body, a protective portion that is lightweight and has excellent heat insulating properties can be formed. Also, material costs can be reduced. Alternatively, the strength may be improved by adding glass fibers or the like. Although the shape of the protection member is not particularly limited, it is usually a cylindrical member or a block-shaped member having a concave portion for receiving the fuel tube. In the case of a tubular member, the fuel tube can be inserted later into a tubular member that has been produced in advance, or the tubular member can be coated and extruded onto the fuel tube so that both are closely attached to each other. To bond the two, an adhesive is applied to the inner surface of the protective member or the concave surface as necessary, and a fuel tube is inserted or fitted into the inner surface, and the two are brought into close contact with each other, whereby the fuel tube and the protective member are integrated. To form a structured structure.
[0094]
The fuel tube of the present invention thus obtained is excellent in alcohol gasoline permeation prevention properties, interlayer adhesion, low-temperature impact resistance, and the like. Therefore, the above characteristics are sufficiently exhibited for fuels such as gasoline, kerosene, diesel gasoline, methanol, ethanol, propanol, butanol, alcohol-containing gasoline, methyl-t-butyl ether, oxygen-containing gasoline, amine-containing gasoline, and sour gasoline. Examples of the tube include a feed tube, a return tube, an evaporation tube, a fuel filler tube, an ORVR tube, a reserve tube, and a vent tube. Particularly, it is preferable as a tube for automobile fuel.
[0095]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
In addition, the physical property measurement in an Example and a comparative example was performed as follows.
[0096]
(Relative viscosity)
According to JIS K6920, it was measured in 96% sulfuric acid under the conditions of a polyamide concentration of 1% and a temperature of 25 ° C.
[0097]
(surface tension)
Using the software “Polymer Material Design Support System EXPOD” manufactured by Mitsubishi Research Institute, it was determined by the above equation.
[0098]
(Evaluation of the physical properties)
(Low temperature impact resistance)
The evaluation was performed according to the method described in SAE J2260.
[0099]
(Alcohol gasoline permeation prevention)
A laminated tube cut to a length of 20 cm is used as a sample. The sample was dried at 110 ° C. for 2 hours and subjected to mass measurement. Then, alcohol / gasoline (hereinafter referred to as CE10) obtained by mixing FuelC (isooctane / toluene = 50/50 volume ratio) and ethanol in a 90/10 volume ratio was used. ) And seal both ends. This is set in a thermostat at 60 ° C., the hose is taken out every 24 hours, and the weight is measured when the temperature returns to room temperature. The change in weight per day divided by the surface area of the inner layer per meter of the tube is divided into the fuel permeability coefficient (g / m²Calculate day).
[0100]
(Interlayer adhesion)
The laminated tube is cut into a length of 20 cm, which is further cut lengthwise and used as a test piece. The outer layer and the inner layer are forcibly peeled off from the end by 1 cm, and the outer layer and the inner layer are sandwiched using a Tensilon universal testing machine as a device to be used, and a 180 ° C. peeling test is performed at a pulling speed of 50 mm / min. The highest strength is read from the maximum point of the SS curve, and is defined as the interlayer adhesive strength (N / cm).
[0101]
[Materials used in Examples and Comparative Examples]
(A) Nylon 12
(A-1) Production of nylon 12 resin composition
USRSTA3030U (manufactured by Ube Industries, relative viscosity 2.27, surface tension 33.8 dyne / cm) was previously mixed with JSR T7712SP (manufactured by JSR) as an impact-improving material, and a twin-screw kneader (manufactured by Japan Steel Works, Ltd.) TYPE, TEX44), while benzenesulfonic acid butylamide was injected as a plasticizer from the middle of the cylinder of the biaxial melt-kneading machine by a metering pump, and melt-kneaded at a cylinder temperature of 180 to 260 ° C. Is extruded into a strand, introduced into a water bath, cooled, cut, and vacuum dried to obtain a nylon 12 resin composition comprising 85% by weight of a nylon 12 resin, 10% by weight of an impact modifier, and 5% by weight of a plasticizer. (Hereinafter, this nylon resin composition is referred to as (A-1)).
[0102]
(A-2) Production of nylon 12 resin composition
In the production method (A-1), UBESTA3030U is changed to UBESTA3020U (manufactured by Ube Industries, relative viscosity 1.86, surface tension 33.8 dyne / cm), and Ketjen Black EC600JD (manufactured by Akzo Nobel) is used as a conductive filler. And a pellet of a nylon 12 resin composition comprising 73% by weight of a nylon 12 resin, 20% by weight of an impact modifier, and 7% by weight of a conductive filler was obtained in the same manner except that no plasticizer was used. The resin composition is referred to as (A-2)).
[0103]
(B) Layered silicate-containing polyamide resin composition
(B-1) Production of Layered Silicate-Containing Polyamide Resin Composition
100 g of montmorillonite having a mean thickness of one unit of the layered silicate of 9.5 mm and a side length of about 0.1 μm is dispersed in 2.3 liters of water, and 28.1 g of 12-aminododecane is added thereto. An acid and 12 ml of concentrated hydrochloric acid were added, and the mixture was stirred at 80 ° C. for 60 minutes. Further, the sufficiently washed product was subjected to suction filtration using a Buchner funnel to obtain a hydrated composite (hereinafter abbreviated as 12MMT). A part of this composite was collected and the water content was determined to be 88%. The interlayer distance of the composite (12MMT) of 12-aminododecanoic acid and montmorillonite was measured by X-ray diffraction and found to be 18 °.
Next, water and caprolactam were added to the 12 MMT so that the ratio became 1: 9: 9, and the mixture was stirred and mixed.
Thereafter, the composite (12MMT) with 12-aminododecanoate montmorillonite was added to 98 parts by weight of a nylon 6/12 copolymer (UBE Nylon 7034B, manufactured by Ube Industries, Ltd., relative viscosity: 3.9). Then, 38 parts by weight of the 12MMT complex to which water and caprolactam are further added is supplied to a twin-screw kneader (manufactured by Nippon Steel Works, Model: TEX44) and melt-kneaded at a cylinder temperature of 210 to 250 ° C., After extruding the molten resin into strands, the molten resin was introduced into a water bath, cooled, cut, and pellets comprising a nylon 6/12 copolymer and a composite were obtained. The pellet was immersed in hot water to remove caprolactam, which is one of the dispersion media in the 12 MMT, and then dried under vacuum to obtain a layered silicate-containing polyamide composition (layered silicate content 2.%). 0% by weight, relative viscosity 3.3, surface tension 42.9 dyne / cm, hereinafter this composition is referred to as (B-1)).
[0104]
(B-2) Production of layered silicate-containing polyamide resin composition
In the production of the above (B-1) layered silicate-containing polyamide resin composition, nylon 6/12 copolymer (UBE Nylon 7034B, relative viscosity 3.9) was converted to nylon 612 (ZYTEL 158 Dopont Co., Ltd.) A layered silicate-containing polyamide composition was obtained in the same manner except that the viscosity was changed to 2.4) (layered silicate content: 2.0% by weight, relative viscosity: 2.1, surface tension: 37.7 dyne / cm, Hereinafter, this composition is referred to as (B-2)).
[0105]
(B-3) Production of layered silicate-containing polyamide resin composition
In the production of the above (B-1) layered silicate-containing polyamide resin composition, the nylon 6/12 copolymer (UBE Nylon 7034B, relative viscosity 3.9) was replaced with the nylon 6/66 copolymer (UBE Nylon 5034B). , Relative viscosity 4.1) to obtain a layered silicate-containing polyamide composition in the same manner (layered silicate content 2.0% by weight, relative viscosity 3.4, surface tension 45.2 dyne / cm, hereinafter this composition is referred to as (B-3)).
[0106]
(B-4) Production of layered silicate-containing polyamide resin composition
In the production of the above (B-1) layered silicate-containing polyamide resin composition, the nylon 6/12 copolymer (UBE Nylon 7034B, relative viscosity 3.9) was replaced with the nylon 6/12 copolymer (UBE Nylon 7125U). , And a relative viscosity of 2.4) to obtain a layered silicate-containing polyamide composition (layer silicate content: 2.0% by weight, relative viscosity: 2.0, surface tension: 36.6 dyne / cm, hereinafter this composition is referred to as (B-4)).
[0107]
(C) Nylon 6
(C-1) Production of Nylon 6 resin composition
JSR T7712SP (manufactured by JSR) is previously mixed with UBE Nylon1024B (manufactured by Ube Industries, relative viscosity: 3.50) as an impact-improving material and supplied to a twin-screw kneader (manufactured by Nippon Steel Works, model: TEX44). Meanwhile, from the middle of the cylinder of the twin-screw melt kneader, benzenesulfonic acid butylamide was injected as a plasticizer by a quantitative pump, melt-kneaded at a cylinder temperature of 230 to 270 ° C., and extruded the molten resin into strands. This was introduced into a water tank, cooled, cut, and vacuum dried to obtain a pellet of a nylon 6 resin composition comprising 75% by weight of a nylon 6 resin, 10% by weight of an impact modifier, and 15% by weight of a plasticizer (hereinafter, referred to as a pellet). This nylon resin composition is called (C-1)).
[0108]
(C-2) Production of nylon 6 resin composition
In the above production method (C-1), UBE Nylon1024B was changed to 1015B (manufactured by Ube Industries, relative viscosity 2.64), and Ketjen Black EC600JD (manufactured by Akzo Nobel) was used in the same manner as the conductive filler. Then, a pellet of a nylon 6 resin composition comprising 60% by weight of a nylon 6 resin, 30% by weight of an impact modifier, 5% by weight of a plasticizer, and 5% by weight of a conductive filler was obtained (hereinafter, this nylon resin composition is referred to as (C- 2)).
[0109]
(D) Modified polyolefin
(D-1) Maleic acid-modified polypropylene Admir QF500 manufactured by Mitsui Chemicals, Inc.
[0110]
Example 1
(A) Nylon 12 resin composition (A-1), (B) layered silicate-containing polyamide resin composition (B-1), (C) Nylon 6 resin composition (C-1) Then, using a three-layer tube molding machine manufactured by Labor, (A) was separately melted at an extrusion temperature of 250 ° C., (B) at an extrusion temperature of 260 ° C., and (C) at an extrusion temperature of 260 ° C., and the melt was discharged. The resins are combined by an adapter, formed into a tube, cooled by a sizing die for controlling the size, taken off, and (A) a layer composed of a nylon 12 resin composition is (a) a layer, and (B) a layered silicate-containing polyamide. When the layer composed of the resin composition is the layer (b) and the layer composed of the nylon 6 resin composition is the layer (c), the layer configuration is (a) / (b) / (c) = 0.35. Product of /0.30/0.35mm, inner diameter 6mm, outer diameter 8mm To obtain a tube. Table 1 shows the measurement results of the physical properties of the laminated tube.
[0111]
Example 2
In Example 1, a laminated tube having a layer configuration shown in Table 1 was prepared in the same manner as in Example 1 except that the layered silicate-containing polyamide resin composition (B-1) was changed to (B-2). Obtained. Table 1 shows the measurement results of the physical properties of the laminated tube.
[0112]
Example 3
In the same manner as in Example 1 except that (C) the polyamide 6 resin composition (C-1) was changed to (C-2) and (C) was melted at an extrusion temperature of 270 ° C. A laminated tube having the layer configuration shown in Table 1 was obtained. Table 1 shows the measurement results of the physical properties of the laminated tube. When the conductivity of the laminated tube was measured in accordance with SAE J-2260,⁶Ω / square or less, and it was confirmed that it was excellent in static electricity removing performance.
[0113]
Example 4
Layers shown in Table 1 in the same manner as in Example 1 except that (C) polyamide 6 resin composition (C-1) was changed to (A) nylon 12 resin composition (A-1). A laminated tube having the configuration was obtained. Table 1 shows the measurement results of the physical properties of the laminated tube.
[0114]
Example 5
In Example 1, except that (C) polyamide 6 resin composition (C-1) was changed to (A) nylon 12 resin composition (A-2) and (A) was melted at an extrusion temperature of 270 ° C. In the same manner as in Example 1, a laminated tube having the layer configuration shown in Table 1 was obtained. Table 1 shows the measurement results of the physical properties of the laminated tube.
[0115]
Example 6
(A) Nylon 12 resin composition (A-1), (B) layered silicate-containing polyamide resin composition (B-1), (C) nylon 6 resin composition (C-1), (C) And (2) using a 4-layer tube molding machine made by Labor, (A) was separately melted at an extrusion temperature of 260 ° C., (B) was melted at an extrusion temperature of 260 ° C., and (C) was melted at an extrusion temperature of 270 ° C. The discharged molten resin is merged by an adapter, formed into a tube, cooled by a sizing die for controlling the size, taken off, and (A) a layer composed of the nylon 12 resin composition is converted into a layer (a) and a layer (B). A) a layer composed of the layered silicate-containing polyamide resin composition, a layer (b), (C) a layer composed of the nylon 6 resin composition (C-1), a layer (c), and (C) a nylon 6 resin composition (C). When the layer composed of -2) is the (c ′) layer, the layer configuration is ( ) / (B) / (c) / (c ') = 0.40 / 0.30 / 0.20 / 0.10mm, an inner diameter of 6 mm, to obtain a laminated tube having an outer diameter of 8 mm. Table 1 shows the measurement results of the physical properties of the laminated tube. When the conductivity of the laminated tube was measured in accordance with SAE J-2260,⁶Ω / square or less, and it was confirmed that it was excellent in static electricity removing performance.
[0116]
Example 7
In Example 6, except that (C) nylon 6 resin composition (C-1) and (C-2) were changed to (A) nylon 12 resin composition (A-1) and (A-2), In the same manner as in Example 6, (A) the layer made of the nylon 12 resin composition (A-1) was used as the (a) layer, and the (A) layer made of the nylon 12 resin composition (A-2) was used as the layer (a ′). ) Layer, and (B) a layer composed of the layered silicate-containing polyamide resin composition as a (b) layer, the layer configuration is (a) / (b) / (a) / (a ′) = 0.40 / A laminated tube having a diameter of 0.30 / 0.20 / 0.10 mm, an inner diameter of 6 mm, and an outer diameter of 8 mm was obtained. Table 1 shows the measurement results of the physical properties of the laminated tube. When the conductivity of the laminated tube was measured in accordance with SAE J-2260,⁶Ω / square or less, and it was confirmed that it was excellent in static electricity removing performance.
[0117]
Comparative Example 1
In Example 1, (B) layered silicate-containing polyamide resin composition (B-1) and (C) nylon 6 resin composition (C-1) were used in the same manner as in Example 1 except that the resin composition was not used. 1 was obtained. Table 1 shows the measurement results of the physical properties of the single-layer tube.
[0118]
Comparative Example 2
In Example 1, except that (B) the layered silicate-containing polyamide resin composition (B-1) was changed to (D) a modified polyolefin (D-1) and (D) was melted at an extrusion temperature of 190 ° C. In the same manner as in Example 1, a laminated tube having the layer configuration shown in Table 1 was obtained. Table 1 shows the measurement results of the physical properties of the laminated tube.
[0119]
Comparative Example 3
A laminated tube having a layer configuration shown in Table 1 in the same manner as in Example 1 except that (B) the layered silicate-containing polyamide resin composition (B-1) was changed to (B-3). Got. Table 1 shows the measurement results of the physical properties of the laminated tube.
[0120]
Comparative Example 4
A laminated tube having a layer configuration shown in Table 1 in the same manner as in Example 1 except that (B) the layered silicate-containing polyamide resin composition (B-1) was changed to (B-4). Got. Table 1 shows the measurement results of the physical properties of the laminated tube.
[0121]
Comparative Example 5
In Example 1, (B) a layered silicate-containing polyamide resin composition (B-1) was used as (B-4), and (C) a nylon 6 resin composition (C-1) was used as (A) a nylon 12 resin composition. Except having changed to the thing (A-1), it carried out similarly to Example 1, and obtained the laminated tube of the layer structure shown in Table 1. Table 1 shows the measurement results of the physical properties of the laminated tube.
[0122]
[Table 1]

[0123]
【The invention's effect】
The fuel tube of the present invention is excellent in heat resistance, chemical resistance, low-temperature impact resistance, alcohol gasoline permeation resistance, and interlayer adhesion. It is particularly suitable as a fuel tube for automobiles.

Claims (7)

(A) a layer (a) composed of polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), and (B1) a polyamide polymer satisfying the following formula (1) and (B2) A) A fuel tube comprising at least two layers (B) comprising a layered silicate-containing polyamide composition in which 0.1 to 30% by weight of a layered silicate is uniformly dispersed.
3.0 ≦ γ _B −γ _A ≦ 10.0 (1)
(Where γ _A (dyne / cm) is (A) the surface tension of polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), and γ _B (dyne / cm) is (B) (Shows the surface tension of the polyamide polymer (B1) in the silicate-containing polyamide composition.) (A) a layer composed of polyundecaneamide (nylon 11) and / or polydodecaneamide (nylon 12), (B) a layer (b) composed of a layered silicate-containing polyamide composition, and (A) polyundecane 2. The method according to claim 1, comprising at least three layers (c) comprising amide (nylon 11) and / or polydodecaneamide (nylon 12) or (C) polycaproamide (nylon 6). Tube for fuel. (A) A layer made of polyundecaneamide (nylon 11) and / or polydodecanamide (nylon 12) is disposed on the outer layer, and (B) a layered silicate-containing polyamide composition inside (B). 3. The fuel tube according to claim 1, wherein the fuel tube has a structure in which layers are arranged. (A) A layer composed of polyundecaneamide (nylon 11) and / or polydodecanamide (nylon 12) is disposed on the outer layer, and (B) a layer composed of a layered silicate-containing polyamide composition is disposed in the middle. The fuel tube according to claim 2 or 3, wherein the fuel tube has a structure in which a layer (c) made of polycaproamide (nylon 6) is disposed in an inner layer. (B) The polyamide polymer (B1) in the layered silicate-containing polyamide composition is a caproamide / dodecaneamide copolymer (nylon 6/12 copolymer) and / or polyhexamethylene dodecamide (nylon 612) The fuel tube according to any one of claims 1 to 4, wherein The fuel tube according to any one of claims 1 to 5, wherein a layer made of a conductive polyamide resin composition containing a conductive filler is disposed as an innermost layer. The fuel tube according to any one of claims 1 to 6, wherein the tube is a vehicle fuel tube.