JP3824905B2 - Antistatic fiber polyester - Google Patents

Description

【００２０】
（式中、Ｒ₁₁，Ｒ₁₂，Ｒ₁₃およびＲ₁₄は同一または異なる炭素数２〜１０個のアルキル基を表し、ｍは１〜３の整数を表す。）
で表されるチタン化合物と下記式（２）
【００２１】
【化６】

【００２２】
（上記式中、Ｒ_２は炭素数２〜１８のアルキル基、または炭素数６〜２０のアリールを表す。）
で表されるリン化合物をチタン元素のモル数に対するリン元素のモル数（Ｐ／Ｔｉ）が１〜４となる範囲の組成でエチレングリコール中で加熱反応せしめたチタン／リン反応物を用い、且つ該ポリエステルに含まれるチタン元素量が全ジカルボン酸残基成分に対し２〜４０ミリモル％の範囲にあり、
Ｂ）該ポリエステルの紡糸工程が完了する以前の任意の段階で、制電剤として、下記式（３）
【００２３】
【化７】

【００２４】
（上記式中、Ｚは１〜６個の活性水素を有する有機化合物残基を、Ｒ₃ は炭素原子数６以上のアルキレン基又は置換アルキレン基を、Ｒ₄ は水素原子、炭素原子数１〜４０の１価の炭化水素基、炭素原子数２〜４０の１価のヒドロキシ炭化水素基又は炭素原子数２〜４０の１価のアシル基を、ｋは１〜６の整数、ｓはｓ≧７０／ｋを満足する整数、ｔは１以上の整数を示す。）
で表されるポリオキシアルキレン系ポリエーテルを、該ポリエステルの重量を基準として、０．２〜３０重量％、および下記式（４）
（Ｒ₅ＳＯ₃）_rＭ （４）
（Ｒ₅は炭素数３〜３０のアルキルアリール基、またはアルキル基で置換されても良い炭素数６〜３０のアリール基を、Ｍはアルカリ金属またはアルカリ土類金属を示す。ｒはＭがアルカリ金属の時は１、Ｍがアルカリ土類金属の時は２を表す。）
で表される有機スルホン酸金属塩を、該ポリエステルの重量を基準として、０．０５〜１０重量％となるように添加し、
Ｃ）下記式（５）
Ｘ＝Ｎ×Ｗ （５）
（上記式においてＮ，Ｗは、それぞれポリエステル２０ｍｇを２枚のプレパラートに挟み、１０ｇ荷重下２８５℃で溶融して直径１ｃｍの薄膜状となした時に観察される直径２．５μｍ以上の粒子の数（個／ｃｍ²）、およびポリエステル組成物中の制電剤の量（ポリエステル１００重量部に対する重量部）を表す。）
で表される該制電剤の分散性Ｘが０．１〜１であり、
Ｄ）並びに固有粘度が０．６５以上である制電性繊維用ポリエステル
によって達成される。
【００２５】
【発明の実施の形態】
以下本発明についてさらに詳細に説明する。
本発明の制電性繊維用ポリエステルは下記式（１）
【００２６】
【化８】

【００２７】
（式中、Ｒ₁₁，Ｒ₁₂，Ｒ₁₃およびＲ₁₄は同一または異なる炭素数２〜１０個のアルキル基を表し、ｍは１〜３の整数を表す。）
で表されるチタン化合物と下記式（２）
【００２８】
【化９】

【００２９】
（上記式中、Ｒ_２は炭素数２〜１８のアルキル基、または炭素数６〜２０のアリールを表す。）
で表されるリン化合物をチタン元素のモル数に対するリン元素のモル数（Ｐ／Ｔｉ）が１〜４となる範囲の組成で反応せしめたチタン／リン反応物を用いて重合されている必要がある。
【００３０】
ここでチタン元素のモル数に対するリン元素のモル数（Ｐ／Ｔｉ）が１より小さい場合、得られるポリエステルの色調が不良になり、かつその耐熱性が低下することがあり好ましくなく、一方４より大きい場合、ポリエステル重合反応に対する触媒活性が不十分になり好ましくない。チタン元素のモル数に対するリン元素のモル数（Ｐ／Ｔｉ）は１．２〜３．５の範囲が好ましく、１．５〜３．０の範囲が更に好ましい。
【００３１】
また、チタン化合物成分（１）とリン化合物成分（２）を反応させるチタン／リン化合物の触媒調製は、エチレングリコール中で加熱反応されている必要があるが、反応方法としては例えばリン化合物（２）からなる成分とエチレングリコールとを混合して、リン化合物成分の一部又は全部をエチレングリコール中に溶解し、この混合液にチタン化合物成分（１）を滴下し、反応系を０℃〜２００℃の温度に３０分間以上、好ましくは６０〜１５０℃の温度に４０〜９０分間、加熱することによって行われる。この反応において、反応圧力については格別の制限はなく、通常常圧下で行われる。
【００３２】
ここで上記式（１）で表されるチタン化合物としては例えば、チタンテトラブトキシド、チタンテトライソプロポキシド、チタンテトラプロポキシド、チタンテトラエトキシドなどのチタンテトラアルコキシドや、オクタアルキルトリチタネート、ヘキサアルキルジチタネート等を挙げることができる。
【００３４】
また上記式（２）で表されるリン化合物としては、例えば、モノアルキルホスフェート等が挙げられ、具体的にはモノメチルホスフェート、モノエチルホスフェート、モノトリメチルホスフェート、モノ−ｎ−ブチルホスフェート、モノヘプチルホスフェート、モノヘキシルホスフェート、モノヘプチルホスフェート、モノノニルホスフェート、モノデシルホスフェート、モノドデシルホスフェート、モノフェニルホスフェート、モノベンジルホスフェート、モノ（４−ドデシル）フェニルホスフェート、モノ（４−メチルフェニル）ホスフェート、モノ（４−エチルフェニル）ホスフェート、モノ（４−プロピルフェニル）ホスフェート、モノ（４−ドデシルフェニル）ホスフェート、モノトリルホスフェート、モノキシリルホスフェート、モノビフェニルホスフェート、モノナフチルホスフェート、モノアントリルホスフェート等が挙げられる。
上記式（１）で表されるチタン化合物は予め下記式（６）
【００３５】
【化１０】

【００３６】
（上記式中、ｑは２〜４の整数を表わす。）
の多価カルボン酸及び／又はその酸無水物と反応させて使用する方法も好ましく用いられる。その場合、チタン化合物と多価カルボン酸及び／又はその酸無水物の反応モル比は（２：１）〜（２：５）の範囲が好ましい。特に好ましい範囲は（１：１）〜（１：２）である。
【００３７】
本発明の制電性繊維用ポリエステルに含まれるチタン元素量は全ジカルボン酸残基成分に対し２〜４０ミリモル％の範囲にあるようにすることが必要である。チタン元素量が２ミリモル％未満の場合は重合反応が遅くなり、４０ミリモル％を超える場合は得られるポリエステルの色調が、不良になり、かつその耐熱性が低下することがあり好ましくない。チタン元素量は５〜３５ミリモル％の範囲が好ましく、１０〜３０ミリモル％の範囲が更に好ましい。
【００３８】
一般的にエチレンテレフタレートを主たる繰り返し単位とするポリエステルの製造方法としては、テレフタル酸に代表される芳香族ジカルボン酸を用いる製造方法とジメチルテレフタレートに代表される芳香族ジカルボン酸のエステル形成性誘導体を原料として用いる二つの方法が知られている。本発明におけるポリエステルは、その製造方法により特に制限はないが、好ましくは原料物質としてジメチルテレフタレートが全ジカルボン酸成分の８０ｍｏｌ％以上である、エステル交換反応を経由する製造方法である。なお本発明においてエチレンテレフタレートを主たる繰り返し単位とするとは全繰り返し単位に対して９０モル％以上がエチレンテレフタレートであることを表す。
【００３９】
なお、上記のジメチルテレフタレートには、本発明方法の効果が実質的に損なわれない範囲内において、具体的には全ジカルボン酸成分合計モル量を基準として１０モル％以下、好ましくは５モル％以下の範囲で、それと共重合可能な他の二官能性カルボン酸エステル等が追加成分として含まれていてもよい。
【００４０】
好ましく用いられる共重合可能な追加成分は、脂肪族および脂環式の二官能性ジカルボン酸類およびこれらのエステル形成性誘導体、ヒドロキシカルボン酸およびこれらのエステル形成性誘導体、並びに脂肪族、脂環式、芳香族のジオール化合物およびポリオキシアルキレングリコール等が挙げられる。例えば、アジピン酸、セバシン酸、１，４−シクロヘキサンジカルボン酸などが脂肪族及び脂環式の二官能性ジカルボン酸およびこれらのエステル形成性誘導体の具体例としてあげられる。またβ−ヒドロキシエトキシ安息香酸、ｐ−オキシ安息香酸などがヒドロキシカルボン酸およびこれらのエステル形成性誘導体の具体例としてあげられる。更に構成炭素数が２個以上のアルキレングリコール、１，４−シクロヘキサンジメタノール、ネオペンチルグリコール、ビスフェノールＡ、ビスフェノールＳ、ポリエチレングリコール等が脂肪族、脂環式、芳香族のジオール化合物およびポリオキシアルキレングリコールの具体例としてあげられる。上記追加成分は一種を単独で用いてもよく、或は二種以上を併用してもよい。ただし共重合比は上記の範囲内であることが必要である。
本発明において制電剤として用いる下記式（３）
【００４１】
【化１１】

【００４２】
（上記式中、Ｚは１〜６個の活性水素を有する有機化合物残基を、Ｒ₃ は炭素原子数６以上のアルキレン基又は置換アルキレン基を、Ｒ₄ は水素原子、炭素原子数１〜４０の１価の炭化水素基、炭素原子数２〜４０の１価のヒドロキシ炭化水素基または炭素原子数２〜４０の１価のアシル基を、ｋは１〜６の整数、ｓはｓ≧７０／ｋを満足する整数、ｔは１以上の整数を示す。）
で表されるポリオキシアルキレン系ポリエーテルの具体例としては、分子量が４０００以上のポリオキシエチレングリコール、分子量が２０００以上のポリオキシプロピレングリコール、ポリオキシテトラメチレングリコール、分子量が２０００以上のエチレンオキシド、プロピレンオキシド共重合体、分子量が４０００以上のトリメチロ−ルプロパンエチレンオキシド付加物、分子量が３０００以上のノニルフェニルエチレンオキシド付加物、並びにこれらの末端水酸基に炭素数が６以上の置換エチレンオキシドが付加した化合物が挙げられる。
【００４３】
該ポリオキシアルキレン系ポリエーテルのポリエステルへの添加量は、繊維重量を基準として、０．２〜３０重量％の範囲に設定する必要がある。該配合量が０．２重量％より少ないと、溶融紡糸して得られた繊維の制電性を十分に得られない。一方、３０重量％より多いと最小制電性の向上効果は認められず、機械的性質が損なわれることとなり好ましくない。
【００４４】
本発明の製造方法においては、制電性を向上させるためには、さらに特定の有機スルホン酸金属塩を配合させる必要がある。
ここで使用する有機スルホン酸金属塩は下記一般式（４）
（Ｒ₅ＳＯ₃）_rＭ （４）
（Ｒ₅は炭素数３〜３０のアルキル基（クレームに同じ）を、Ｍはアルカリ金属またはアルカリ土類金属を示す。ｒはＭがアルカリ金属の時は１、Ｍがアルカリ土類金属の時は２を表す。）
で表わされる。上記式（４）においてＲ₅としてアルキル基を用いる場合は、直鎖状であっても、また側鎖を有してもよい。なおポリエステルとの相溶性の観点から、Ｒがアルキル基、アルキルアリール基以外の有機スルホン酸金属塩は好ましくない。
【００４５】
ＭはＮａ、Ｋ、Ｌｉ等のアルカリ金属、Ｍｇ、Ｃａ等のアルカリ土類金属等が挙げられ、なかでもＮａ、Ｋが好ましい。なお、有機スルホン酸金属塩の使用に際しでは、単一の化合物である必要はなく、各種のアルキル基を有する有機スルホン酸金属塩の混合物であってもよい。
【００４６】
このような有機スルホン酸金属塩としては具体的には、ステアリルスルホン酸ナトリウム、オクチルスルホン酸ナトリウム、ドデシルスルホン酸ナトリウム、ステアリルベンゼンスルホン酸ナトリウム、オクチルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウムまたは炭素数の平均が１４個であるアルキルスルホン酸ナトリウムの混合物等が好ましいものとして挙げられる。
【００４７】
該有機スルホン酸金属塩のポリエステルへの添加量は、繊維重量を基準として、０．０５〜１０重量％の範囲にある必要がある。該配合量が０．０５重量％より少ないと、溶融紡糸して得られたポリエステル繊維の制電性が充分でなく、１０重量％より多いと混合操作、紡糸等が困難となるので好ましくない。
【００４８】
このようなポリオキシアルキレン系ポリエーテル、および有機スルホン酸金属塩の制電剤は紡糸工程完了以前の任意の段階でポリエステルに添加配合される。例えば、ポリエステル製造の原料に予め添加しても、ポリエステル重合の第１段重合反応時またはこれに続く第２段の重合反応時に添加することも可能であり、また重縮合反応後に得られるポリエステルと制電剤とを、例えば溶融押出機を用いて溶融混合する方法、溶融成形機の出口以前の段階でポリエステルに添加し混合する方法等を採用することも可能である。またポリオキシアルキレン系ポリエーテルと有機スルホン酸金属塩を別の工程で添加しても構わない。
また本発明で下記式（５）
Ｘ＝Ｎ×Ｗ （５）
（上記式においてＮ，Ｗは、それぞれポリエステル２０ｍｇを２枚のプレパラートに挟み、１０ｇ荷重下２８５℃で溶融して直径１ｃｍの薄膜状となした時に観察される直径２．５μｍ以上の粒子の数（個／ｃｍ²）、およびポリエステル組成物中の制電剤の量（ポリエステル１００重量部に対する重量部）を表す。）
で表される該制電剤の分散性Ｘが０．１〜１である。好ましくは０．２以上０．５以下である。
【００４９】
上記式で定義される分散性Ｘが０．１未満である場合には、制電剤が極度に微分散化されており、かかる組成物から得られる繊維の制電性能は不十分となり好ましくない。一方、分散性が１．０を超える場合には、制電剤の分散が不十分となり、制電剤がチップ表面や繊維表面に滲み出しやすくなる。このため、チップをエクストルーダーで溶融紡糸する際には、チップの噛み込み不良を引き起こし、また繊維に対しては制電性能の低下を引き起こす。
【００５０】
制電剤を配合したポリエステルを紡糸するに当たっては、特別な条件を採用する必要はなく、任意の溶融紡糸条件を採用することが可能である。なお、本発明の製造方法において、繊維の断面形態は、本発明の目的とする効果を奏する限り任意に選択することができ、丸形、異形など、適宜選択すればよく、また断面の大きさ（繊度）にも制限はない。
【００５１】
また、本発明の製造方法において得られるポリエステル繊維には必要に応じて触媒、着色防止剤、耐熱剤、蛍光剤、難燃剤、染料、顔料、不活性微粒子等が含まれていてもよい。
【００５２】
さらに、得られるポリエステルの色調を微調整するために、反応系にポリエステルの製造段階において、アゾ系、トリフェニルメタン系、キノリン系、アントラキノン系、フタロシアニン系等の有機青色顔料及び無機青色顔料の一種以上からなる整色剤を添加することができる。なお、本発明の製造方法においては、当然のことながらポリエステルの溶融熱安定性を低下させるコバルト等を含む無機青色顔料を整色剤としては用いる必要はなく、したがって得られるポリエステルには実質的にコバルトを含まないことが好ましい。
【００５３】
本発明方法によって得られるポリエステルは、通常、ハンター型色差計より得られるＬ値が８０．０以上、ｂ値が−２．０〜５．０の範囲にあるものである。ポリエステルのＬ値が８０．０未満であると、白色度が低くなるため実用に供し得る高白色度成形物を得ることができないことがある。また、ｂ値が−２．０未満であると、このポリエステルの青味が増し、一方、ｂ値が５．０を越えると、得られるポリエステルの黄味が強くなるため、実用上有用な成形物の製造に供することができないことがある。本発明方法により得られるポリエステルのＬ値は好ましくは８２以上、特に好ましくは８３以上であり、ｂ値の好ましい範囲は−１．０〜４．５であり、特に好ましくは０．０〜４．０である。
【００５４】
なお、本発明方法により得られるポリエステルのＬ値及びｂ値は、下記の方法により測定される。すなわち、ポリエステルの試料を２９０℃、真空下で１０分間溶融し、これをアルミニウム板上において、厚さ３．０±１．０ｍｍのプレートに成形し、このプレートをただちに氷水中で急冷し、このプレートを１６０℃、１時間乾燥し、次に結晶化処理を施し、その後、プレートを色差計調整用の白色標準プレート上に置き、供試プレート表面の色調を、ミノルタ社製ハンター型色差計ＣＲ−２００を用いて測定した。
【００５５】
本発明のポリエステルは、実質的に、整色用コバルト化合物に由来するコバルト原子を含まないものである。コバルト原子を含むポリエステルには、溶融熱安定性が低く、分解が起こりやすくなるという欠点がある。なお、ここで“実質的に含まない”とは、整色剤若しくは重縮合触媒としてコバルト化合物を使用せず、したがって、得られるポリエステルが、上記コバルト化合物に由来するコバルト原子を含まないことを意味する。したがって、本発明のポリエステルは、整色剤及び触媒以外の目的をもって添加されたコバルト化合物に由来するコバルト原子を含むことがあってもよい。
【００５６】
本発明におけるポリエステルの固有粘度は適宜選択すればよいが、０．５５〜１．０の範囲にあることが好ましい。該固有粘度がこの範囲内にあると、溶融成形が容易でかつ成形物の強度も高いものとなる。該固有粘度のさらに好ましい範囲は、０．６０〜０．９０であり、特に好ましくは０．６２〜０．８０である。
【００５７】
【実施例】
本発明をさらに下記実施例により具体的に説明するが、本発明の範囲はこれら実施例により限定されるものではない。ただし上述の通り、固有粘度、色相、チタン含有量、分散性、紡糸口金に発生する付着物の層及び制電耐久性については、下記記載の方法により測定された。
【００５８】
１）固有粘度：
ポリエステルの固有粘度は、オルソクロロフェノール溶液について、３５℃において測定した粘度の値から求めた。
【００５９】
２）色調（Ｌ値及びｂ値）：
ポリエステル試料を２９０℃、真空下で１０分間溶融し、これをアルミニウム板上で厚さ３．０±１．０ｍｍのプレートに成形後ただちに氷水中で急冷し、該プレートを１６０℃、１時間乾燥結晶化処理後、色差計調整用の白色標準プレート上に置き、プレート表面のハンターＬ値及びｂ値を、ミノルタ社製ハンター型色差計ＣＲ−２００を用いて測定した。Ｌ値は明度を示し、その数値が大きいほど明度が高いことを示し、ｂ値はその値が大きいほど黄着色の度合いが大きいことを示す。
【００６０】
３）触媒のチタン含有量：
触媒化合物中のチタン濃度は、リガク社製蛍光Ｘ線測定装置３２７０を用いて測定した。
【００６１】
４）紡糸口金に発生する付着物の層：
ポリエステルをチップとなし、これを２９０℃で溶融し、孔径０．１５ｍｍφ、孔数１２個の紡糸口金から吐出し、６００ｍ／分で２日間紡糸し、口金の吐出口外縁に発生する付着物の層の高さを測定した。この付着物層の高さが大きいほど吐出されたポリエステルメルトのフィラメント状流にベンディングが発生しやすく、このポリエステルの成形性は低くなる。すなわち、紡糸口金に発生する付着物層の高さは、当該ポリエステルの成形性の指標である。
【００６２】
５）制電耐久性：
得られたポリエステル繊維を用いて作製した編物を、アニオン性洗剤（花王石鹸（株）製「ザブ」）の０．３％水溶液を用いて家庭用電気洗濯機にて４０℃、３０分間洗濯した後、編物を乾燥させた。
【００６３】
乾燥後の試料を水中に３０分間以上浸漬させた後、家庭用電気洗濯機の脱水機で５分間脱水した。上記洗濯前後のサンプルを２５℃、相対湿度６５％で一昼夜放置した後の比抵抗値を測定した。
【００６４】
６）制電剤の分散性Ｘ
得られたポリエステル２０ｍｇを２枚のプレパラートに挟み、１０ｇ荷重下２８５℃で溶融して直径１ｃｍの薄膜状となした時に観察される直径２．５μｍ以上の粒子の数（個／ｃｍ²）、およびポリエステル組成物中の制電剤の量（ポリエステル１００重量部に対する重量部）を表す。
【００６５】
［参考例１］
１）触媒（Ａ）の調製：
エチレングリコール２．５重量部に無水トリメリット酸０．８重量部を溶解し、この溶液にチタンテトラブトキシド０．７重量部（無水トリメリット酸のモル量を基準として０．５ｍｏｌ％）を滴下し、この反応系を空気中、常圧下、８０℃に６０分間保持してチタンテトラブトキシドと無水トリメリット酸とを反応させ、反応生成物を熟成させた。その後反応系を常温に冷却し、これにアセトン１５重量部を加え、析出物をＮｏ．５ろ紙で濾過し、採取し、これを１００℃の温度で２時間乾燥した。得られた反応生成物（チタン化合物（２））のチタン含有量は１１．２重量％であった。
【００６６】
次に、エチレングリコール１３１重量部中にフェニルホスホン酸３．６重量部を１２０℃に１０分間加熱して溶解した。このエチレングリコール溶液１３４．５重量部に、さらにエチレングリコール４０重量部を加えた後、これに上記チタン化合物（２）５．０重量部を溶解させた。得られた反応系を１２０℃で６０分間撹拌し、チタン化合物（２）とフェニルホスホン酸とを反応させ、反応生成物を含む触媒（Ａ）の白色スラリーを得た。この触媒（Ａ）スラリーのチタン含量は０．３重量％であった。
【００６７】
２）ポリエステルの製造：
テレフタル酸１６６重量部とエチレングリコール７５重量部とを２４０℃においてエステル化反応させ、次いで得られた反応生成物を精留塔付き重縮合用フラスコへ入れ、重縮合触媒として上記触媒（Ａ）スラリー０．９５重量部（テレフタル酸のモル量を基準として、チタン原子のモル量換算で２０×１０^-3モル％）及び整色剤としてテラゾールブルー０．０００２重量部を加えた。
【００６８】
温度２８５℃、常圧で３０分間加熱し、温度２８０℃、大気圧下で３０分間反応させ、次いで４．０ｋＰａ（３０ｍｍＨｇ）の減圧下で１５分間反応させた後、一旦大気圧下に戻し、下記化学式（７）
【００６９】
【化１２】

【００７０】
（但し、ｊは１８〜２８の整数で平均２１、Ｐは平均値として１００、ｍは平均値として５である。）
で表されるポリオキシエチレン系ポリエーテルを８部、炭素数８〜２０で平均炭素数が１４であるアルキルスルホン酸ナトリウムの混合物を１０部添加した後、系内を徐々に減圧し、撹拌下８０分間反応させた。最終内温は２８０℃、最終内圧は４２．７Ｐａ（０．３２ｍｍＨｇ）であり、得られたポリエステルの固有粘度は０．６５０であった。
【００７１】
反応終了後ポリエステルを常法に従いチップ化し、乾燥した。なおポリエステル中のポリオキシエチレン系ポリエーテルとアルキルスルホン酸ナトリウムの添加量はそれぞれ２．５重量％、３重量％であり、分散性Ｘは０．８３であった。次にこの乾操したチップを用い、常法にしたがって３３３ｄｔｅｘ／３６ｆｉｌの原糸を作り、４．０倍に延伸して８３．２５ｄｔｅｘ／３６ｆｉｌのマルチフィラメントを得た。このフィラメントからメリヤス編地を得た。結果を表１、表２に示す。
【００７２】
［参考例２］
１）ポリエステルの製造：
テレフタル酸ジメチル１９４重量部、エチレングリコール１２４重量部及び酢酸カルシウム０．１２重量部を精留塔付き反応槽に投入し、２２０℃においてエステル交換反応を行い、生成した理論量のメタノールを留出除去した後、この反応混合物にリン酸０．０９重量部を加えて第１段階の反応を終了した。次いで前記反応混合物を精留塔付き重縮合用フラスコへ入れ、この反応混合物に、重縮合触媒として、参考例１と同じ方法により得られた触媒（Ａ）スラリー３．２重量部（テレフタル酸ジメチルのモル量を基準として、チタン化合物（２）の含有量はチタン原子モル量換算で２０×１０^−３モル％）、及び整色剤としてテラゾールブルー０．０００２重量部を加えた。
【００７３】
この反応系を温度２８０℃、大気圧下で３０分間反応させ、次いで４．０ｋＰａ（３０ｍｍＨｇ）の減圧下で１５分間反応させた後、一旦大気圧下に戻し、上記式（６）で表されるポリオキシエチレン系ポリエーテルを８部、炭素数８〜２０で平均炭素数が１４であるアルキルスルホン酸ソーダの混合物を１０部添加した後、系内を徐々に減圧し、撹拌下８０分間反応させた。最終内温は２８０℃、最終内圧は４２．７Ｐａ（０．３２ｍｍＨｇ）であり、得られたポリエステルの固有粘度は０．６５１であった。なお、反応終了後ポリエステルを常法に従いチップ化し、乾燥した。なおポリエステル中のポリオキシエチレン系ポリエーテルとアルキルスルホン酸ナトリウムの添加量はそれぞれ２．５重量％、３重量％であり、分散性Ｘは０．７４であった。次にこの乾操したチップを用い、常法にしたがって３３３ｄｔｅｘ／３６ｆｉｌの原糸を作り、４．０倍に延伸して８３．２５ｄｔｅｘ／３６ｆｉｌのマルチフィラメントを得た。結果を表１、表２に示す。
【００７４】
［参考例３］
１）ポリエステルの製造：
参考例２において、ポリオキシアルキレングリコール系ポリエーテルを分子量４０００のポリオキシエチレングリコール８部、有機スルホン酸金属塩を炭素数８〜２０で平均炭素数が１２であるアルキルスルホン酸ソーダ９部に変更する以外は同様にして重縮合反応を行いポリエステル及び繊維を得た。結果を表１、表２に示す。なおポリエステル中のポリオキシエチレン系ポリエーテルとアルキルスルホン酸ナトリウムの添加量はそれぞれ２．５重量％、３重量％であった。
【００７５】
［実施例１〜３］
１）ポリエステルの製造：
参考例１において、リン化合物を表１示す化合物及び値に変更する以外は同様にして重縮合反応を行いポリエステル及び繊維を得た。結果を表１、表２に示す。なおこれらの実施例においてポリエステル中のポリオキシエチレン系ポリエーテルとアルキルスルホン酸ナトリウムの添加量はそれぞれ２．５重量％、３重量％であった。
【００７６】
［比較例１］
参考例２のポリエステルの製造法と同様にしてポリエステルを製造した。ただし、重縮合触媒として、チタンテトラブトキシドのみを用い、この触媒の添加量を、テレフタル酸ジメチルのモル量を基準として、チタン原子モル量換算で２０×１０^−３％となるように、触媒スラリーの濃度及び添加量を調整した。結果を表１、表２に示す。
【００７７】
［比較例２］
１）触媒（Ｂ）の調製：
無水トリメリット酸０．８０重量部をエタノールに溶解し、この溶液にチタンテトラブトキシド０．６４重量部を滴下し、得られた反応系を空気中、常圧の下、８０℃の温度に６０分間保持して、チタンテトラブトキシドとトリメリット酸無水物とを反応させ、熟成した。反応熟成後、反応系を常温に冷却し、これにアセトン１５重量部を加え、生成した沈殿を濾取した。このようにして得られた触媒（Ｂ）のチタン含量は１１．３重量％であった。
【００７８】
２）ポリエステルの製造：
参考例２のポリエステルの製造法と同様にしてポリエステルを製造した。ただし、重縮合触媒として、上記触媒（Ｂ）を用い、この触媒（Ｂ）の添加量が、テレフタル酸ジメチルのモル量を基準としてチタン原子モル量換算で２０×１０^−３モル％となるようスラリーの触媒濃度及び添加量を調整した。結果を表１、表２に示す。
【００７９】
［比較例３］
参考例２のポリエステルの製造法と同様にして、ポリエステルを製造した。ただし、重縮合触媒として、三酸化アンチモンを用い、この触媒の添加量を、テレフタル酸ジメチルのモル量を基準として、アンチモン原子モル量換算で２５×１０^−３％となるようスラリーの濃度及び添加量を調整した。結果を表１、表２に示す。
【００８０】
[比較例４〜６]
比較例１〜３において、ポリオキシアルキレングリコール系ポリエーテルを分子量４０００のポリオキシエチレングリコール８部、有機スルホン酸金属塩を炭素数８〜２０で平均炭素数が１２であるアルキルスルホン酸ソーダ９部に変更する以外は同様にして重縮合反応を行いポリエステル及び繊維を得た。結果を表１、表２に示す。
【００８１】
【表１】

【００８２】
【表２】

【００８３】
【発明の効果】
本発明の制電性繊維用ポリエステルによれば、良好な色調（ｂ値）を有し、かつ優れた制電性を呈するポリエステルを提供することができ、さらに本発明方法により得られたポリエステルは、紡糸口金を通して長時間連続的に紡糸しても口金付着物の発生量が非常に少なく、成形性に優れているという優れた性能を有するものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester for antistatic fibers, and more specifically, has a good color tone (b value) using a polyester production catalyst containing a specific titanium compound and a phosphorus compound, and has excellent antistatic properties. In addition, even if spinning is continued for a long time through the spinneret, the amount of deposits on the die is very small, and a polyester excellent in moldability can be provided.
[0002]
[Prior art]
Polyesters, especially polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate and polytetramethylene terephthalate are widely used in fibers, films and other molded products because of their excellent mechanical, physical and chemical performance. Yes.
[0003]
For example, polyethylene terephthalate is usually obtained by direct esterification of terephthalic acid and ethylene glycol, transesterification of lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, or terephthalic acid and ethylene oxide. The reaction product is produced by producing an ethylene glycol ester of terephthalic acid and / or a low polymer thereof, and then heating the reaction product under reduced pressure in the presence of a polymerization catalyst until a predetermined polymerization degree is reached. ing. Polyethylene naphthalate, polytrimethylene terephthalate, and polytetramethylene terephthalate are also produced by the same method as described above.
[0004]
It is well known that the reaction rate and the quality of the resulting polyester are greatly affected by the type of catalyst used in these polymerization reaction stages. As a polymerization catalyst for polyethylene terephthalate, an antimony compound is most widely used because it has excellent polymerization catalyst performance and a polyester having a good color tone can be obtained.
[0005]
However, when an antimony compound is used as a polymerization catalyst, when the polyester is continuously melt-spun for a long time, foreign matter (hereinafter, sometimes referred to simply as a base foreign matter) adheres and accumulates around the mouthpiece hole, and the flow of the molten polyester flows. The bending phenomenon (bending) occurs, and this causes a problem of formability that fuzz and / or yarn breakage occurs in the spinning / drawing process.
[0006]
As a polymerization catalyst other than the antimony compound, it has also been proposed to use a titanium compound such as titanium tetrabutoxide, but when such a titanium compound is used, the moldability resulting from the deposition of a foreign substance in the die as described above. This problem can be solved, but there arises a new problem that the obtained polyester itself is colored yellow and the heat stability of the melt is poor.
[0007]
In order to solve the above-mentioned coloring problem, it is generally performed to add a cobalt compound to polyester to suppress yellowing. Certainly, the color tone (b value) of the polyester can be improved by adding a cobalt compound, but the problem that the addition of a cobalt compound decreases the melt heat stability of the polyester and also tends to cause degradation of the polyester. There is.
[0008]
As other titanium compounds, Japanese Patent Publication No. 48-2229 discloses the use of titanium hydroxide, and Japanese Patent Publication No. 47-26597 uses α-titanic acid as a catalyst for producing polyester. ing. However, in the former method, powdering of titanium hydroxide is not easy, while in the latter method, α-titanic acid is likely to be altered, so that it is not easy to store and handle it. Is not suitable, and it is also difficult to obtain a polyester having a better color tone (b value).
[0009]
JP-B-59-46258 discloses a product obtained by reacting a titanium compound with trimellitic acid, and JP-A-58-38822 discloses a reaction between a titanium compound and a phosphite. It is disclosed that each of the products obtained in this manner is used as a catalyst for producing a polyester. Certainly, according to this method, although the melt heat stability of the polyester is improved to some extent, the color tone of the obtained polyester is not sufficient, and therefore further improvement of the polyester color tone is desired.
[0010]
Furthermore, in JP-A-7-138354, it has been proposed to use a complex of a titanium compound and a phosphorus compound as a catalyst for producing a polyester. According to this method, the heat of fusion stability is improved to some extent, The color tone of the resulting polyester is not sufficient.
[0011]
In addition, these titanium / phosphorous catalysts themselves often remain as foreign matters in the polyester polyester, and as a result, there is a problem that yarn breakage is likely to occur in the spinning / drawing process, and this problem is also solved. It was hoped that it would be done.
[0012]
In general, when polyester is used as a fiber, the resulting fiber itself is easily charged with static electricity and has a drawback of poor antistatic properties. As a conventional method for imparting antistatic properties to a polyester fiber, a method of blending a polyalkylene ether or a polyalkylene ether and an organic sulfonic acid metal salt into a polyester at a stage before yarn production (Japanese Patent Publication No. 44-31828, Japanese Patent Publication No. Sho) 60-11944, JP-A-3-139556, etc.) have been proposed.
[0013]
However, when the polyester chips obtained by these methods are melt-spun by remelting with a rudder, the chip slips on the rudder, resulting in a problem of biting failure, and it is difficult to stably melt-spin. was there.
[0014]
For this reason, as a method for improving the stability of melt spinning and obtaining a polyester excellent in antistatic properties, a method of regulating the dispersion state of the antistatic agent in the polyester within a specific range (Japanese Patent No. 3130624) Proposed. Certainly, this method eliminates the problem of poor melt spinning stability. However, the fiber using such polyethylene terephthalate is soft due to its chemical modification, and due to the occurrence of foreign matter in the die as in the case of using the above-described antimony compound as a catalyst during melt spinning. There is a problem that productivity tends to decrease.
[0015]
The problem of the base foreign matter can be solved by using another catalyst system without using the antimony compound as described above. However, the method that does not use an antimony compound cannot actually be used because the color tone of the yarn is lowered. Accordingly, there has been a demand for an antistatic fiber polyester which is less likely to generate foreign matter in the die, has excellent color tone, is excellent in hygroscopicity and water absorption, and has excellent moldability.
[0016]
[Problems to be solved by the invention]
An object of the present invention is to have a good color tone (b value) using a catalyst for producing a polyester containing a specific titanium compound and a phosphorus compound, exhibit excellent antistatic properties, and further pass through a spinneret. An object of the present invention is to provide a polyester fiber which has a very small amount of deposits on the die even when spinning continuously for a long time and has excellent moldability.
[0017]
[Means for Solving the Problems]
As a result of intensive studies in view of the above prior art, the present inventors have completed the present invention.
[0018]
That is, the present invention
1. It consists of polyester with ethylene terephthalate as the main repeating unit,
A) As a catalyst at the time of polyester polymerization, the following formula (1)
[0019]
[Chemical formula 5]

[0020]
(Wherein R₁₁, R₁₂, R₁₃And R₁₄Represent the same or different alkyl groups having 2 to 10 carbon atoms, and m represents an integer of 1 to 3. )
And the following formula (2)
[0021]
[Chemical 6]

[0022]
(In the above formula, R₂Is an alkyl group having 2 to 18 carbon atoms, or aryl having 6 to 20 carbon atomsRepresents. )
Using a titanium / phosphorus reactant obtained by heat-reacting a phosphorus compound represented by the formula (1) in a composition in which the number of moles of phosphorus element relative to the number of moles of titanium element (P / Ti) is 1 to 4, and in ethylene glycol; The amount of titanium element contained in the polyester is in the range of 2 to 40 mmol% with respect to the total dicarboxylic acid residue component,
B) As an antistatic agent at an arbitrary stage before the spinning process of the polyester is completed, the following formula (3)
[0023]
[Chemical 7]

[0024]
(In the above formula, Z represents an organic compound residue having 1 to 6 active hydrogens, R_Three Represents an alkylene group having 6 or more carbon atoms or a substituted alkylene group, R_Four Is a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms, a monovalent hydroxy hydrocarbon group having 2 to 40 carbon atoms, or a monovalent acyl group having 2 to 40 carbon atoms, k is 1 An integer of ˜6, s is an integer satisfying s ≧ 70 / k, and t is an integer of 1 or more. )
The polyoxyalkylene polyether represented by the formula: 0.2 to 30% by weight based on the weight of the polyester, and the following formula (4)
(R_FiveSO_Three)_rM (4)
(R_FiveRepresents an alkylaryl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms which may be substituted with an alkyl group, and M represents an alkali metal or an alkaline earth metal. r represents 1 when M is an alkali metal, and 2 when M is an alkaline earth metal. )
An organic sulfonic acid metal salt represented by the formula (I) is added so as to be 0.05 to 10% by weight based on the weight of the polyester,
C) The following formula (5)
X = N × W (5)
(In the above formula, N and W are the number of particles having a diameter of 2.5 μm or more observed when 20 mg of polyester is sandwiched between two preparations and melted at 285 ° C. under a load of 10 g to form a thin film having a diameter of 1 cm. (Pieces / cm²) And the amount of antistatic agent in the polyester composition (parts by weight relative to 100 parts by weight of the polyester). )
Dispersibility X of the antistatic agent represented by the formula is 0.1 to 1,
D) Polyester for antistatic fibers having an intrinsic viscosity of 0.65 or more
Achieved by:
[0025]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in further detail below.
The polyester for antistatic fibers of the present invention has the following formula (1):
[0026]
[Chemical 8]

[0027]
(Wherein R₁₁, R₁₂, R₁₃And R₁₄Represent the same or different alkyl groups having 2 to 10 carbon atoms, and m represents an integer of 1 to 3. )
And the following formula (2)
[0028]
[Chemical 9]

[0029]
(In the above formula, R₂Is an alkyl group having 2 to 18 carbon atoms, or aryl having 6 to 20 carbon atomsRepresents. )
Must be polymerized using a titanium / phosphorus reactant obtained by reacting the phosphorus compound represented by the formula (1) with a composition in which the molar number of phosphorus element (P / Ti) is 1 to 4 with respect to the molar number of titanium element. is there.
[0030]
Here, if the number of moles of phosphorus element (P / Ti) relative to the number of moles of titanium element is less than 1, the color tone of the resulting polyester may be poor and the heat resistance may be lowered. If it is large, the catalyst activity for the polyester polymerization reaction becomes insufficient, which is not preferable. The number of moles of phosphorus element (P / Ti) relative to the number of moles of titanium element is preferably in the range of 1.2 to 3.5, and more preferably in the range of 1.5 to 3.0.
[0031]
In addition, the catalyst preparation of the titanium / phosphorus compound in which the titanium compound component (1) and the phosphorus compound component (2) are reacted needs to be heat-reacted in ethylene glycol. ) And ethylene glycol are mixed, and part or all of the phosphorus compound component is dissolved in ethylene glycol. The titanium compound component (1) is added dropwise to the mixture, and the reaction system is heated to 0 ° C to 200 ° C. It is carried out by heating to a temperature of 30 ° C. for 30 minutes or more, preferably to a temperature of 60 to 150 ° C. for 40 to 90 minutes. In this reaction, the reaction pressure is not particularly limited and is usually carried out under normal pressure.
[0032]
Here, examples of the titanium compound represented by the above formula (1) include titanium tetraalkoxides such as titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide, and titanium tetraethoxide, octaalkyltrititanate, and hexaalkyl. And dititanate.
[0034]
  Moreover, as a phosphorus compound represented by the said Formula (2),Examples thereof include monoalkyl phosphates, and specifically include monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monoheptyl phosphate, monohexyl phosphate, monoheptyl phosphate, monononyl phosphate, monodecyl phosphate Phosphate, monododecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono (4-dodecyl) phenyl phosphate, mono (4-methylphenyl) phosphate, mono (4-ethylphenyl) phosphate, mono (4-propylphenyl) phosphate, Mono (4-dodecylphenyl) phosphate, monotolyl phosphate, monoxyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate Eto, include the mono-en-tolyl phosphate and the like.
  The titanium compound represented by the above formula (1) has the following formula in advance.(6)
[0035]
[Chemical Formula 10]

[0036]
(In the above formula, q represents an integer of 2 to 4.)
A method of reacting with a polyvalent carboxylic acid and / or an acid anhydride thereof is also preferably used. In that case, the reaction molar ratio of the titanium compound and the polyvalent carboxylic acid and / or its acid anhydride is preferably in the range of (2: 1) to (2: 5). A particularly preferable range is (1: 1) to (1: 2).
[0037]
The amount of titanium element contained in the antistatic fiber polyester of the present invention needs to be in the range of 2 to 40 mmol% with respect to the total dicarboxylic acid residue component. When the amount of elemental titanium is less than 2 mmol%, the polymerization reaction is slow, and when it exceeds 40 mmol%, the color tone of the resulting polyester is unsatisfactory and its heat resistance is lowered. The amount of titanium element is preferably in the range of 5 to 35 mmol%, more preferably in the range of 10 to 30 mmol%.
[0038]
Generally, as a method for producing a polyester having ethylene terephthalate as a main repeating unit, a production method using an aromatic dicarboxylic acid typified by terephthalic acid and an ester-forming derivative of an aromatic dicarboxylic acid typified by dimethyl terephthalate are used as raw materials. Two methods used as are known. The polyester in the present invention is not particularly limited depending on its production method, but is preferably a production method via a transesterification reaction in which dimethyl terephthalate is 80 mol% or more of the total dicarboxylic acid component as a raw material. In the present invention, ethylene terephthalate as the main repeating unit means that 90 mol% or more of ethylene terephthalate is based on all repeating units.
[0039]
In the above dimethyl terephthalate, within the range in which the effect of the method of the present invention is not substantially impaired, specifically, 10 mol% or less, preferably 5 mol% or less, based on the total molar amount of all dicarboxylic acid components. In this range, other bifunctional carboxylic acid ester copolymerizable therewith may be included as an additional component.
[0040]
Additional copolymerizable components preferably used include aliphatic and cycloaliphatic difunctional dicarboxylic acids and their ester-forming derivatives, hydroxycarboxylic acids and their ester-forming derivatives, and aliphatic, cycloaliphatic, Aromatic diol compounds and polyoxyalkylene glycols can be mentioned. For example, adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid and the like are specific examples of aliphatic and alicyclic difunctional dicarboxylic acids and ester-forming derivatives thereof. Further, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid and the like are specific examples of hydroxycarboxylic acids and ester-forming derivatives thereof. Further, alkylene glycols having 2 or more carbon atoms, 1,4-cyclohexanedimethanol, neopentyl glycol, bisphenol A, bisphenol S, polyethylene glycol and the like are aliphatic, alicyclic, aromatic diol compounds and polyoxyalkylenes. Specific examples of glycols are listed. The above additional components may be used alone or in combination of two or more. However, the copolymerization ratio needs to be within the above range.
The following formula (3) used as an antistatic agent in the present invention
[0041]
Embedded image

[0042]
(In the above formula, Z represents an organic compound residue having 1 to 6 active hydrogens, R_Three Represents an alkylene group having 6 or more carbon atoms or a substituted alkylene group, R_Four Is a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms, a monovalent hydroxy hydrocarbon group having 2 to 40 carbon atoms, or a monovalent acyl group having 2 to 40 carbon atoms, k is 1 An integer of ˜6, s is an integer satisfying s ≧ 70 / k, and t is an integer of 1 or more. )
Specific examples of the polyoxyalkylene polyether represented by the formula are polyoxyethylene glycol having a molecular weight of 4000 or more, polyoxypropylene glycol having a molecular weight of 2000 or more, polyoxytetramethylene glycol, ethylene oxide having a molecular weight of 2000 or more, propylene Examples thereof include oxide copolymers, trimethylolpropane ethylene oxide adducts having a molecular weight of 4000 or more, nonylphenylethylene oxide adducts having a molecular weight of 3000 or more, and compounds in which a substituted ethylene oxide having 6 or more carbon atoms is added to these terminal hydroxyl groups. .
[0043]
The amount of the polyoxyalkylene polyether added to the polyester needs to be set in the range of 0.2 to 30% by weight based on the fiber weight. If the blending amount is less than 0.2% by weight, the antistatic property of the fiber obtained by melt spinning cannot be obtained sufficiently. On the other hand, if it exceeds 30% by weight, the effect of improving the minimum antistatic property is not recognized, and the mechanical properties are impaired.
[0044]
In the production method of the present invention, in order to improve antistatic properties, it is necessary to further blend a specific organic sulfonic acid metal salt.
The organic sulfonic acid metal salt used here is represented by the following general formula (4).
(R_FiveSO_Three)_rM (4)
(R_FiveRepresents an alkyl group having 3 to 30 carbon atoms (the same as in the claims), and M represents an alkali metal or an alkaline earth metal. r represents 1 when M is an alkali metal, and 2 when M is an alkaline earth metal. )
It is represented by In the above formula (4), R_FiveIn the case where an alkyl group is used, it may be linear or have a side chain. From the viewpoint of compatibility with polyester, organic sulfonic acid metal salts other than those in which R is an alkyl group or an alkylaryl group are not preferred.
[0045]
Examples of M include alkali metals such as Na, K, and Li, and alkaline earth metals such as Mg and Ca. Among these, Na and K are preferable. In addition, when using the organic sulfonic acid metal salt, it is not necessary to be a single compound, and a mixture of organic sulfonic acid metal salts having various alkyl groups may be used.
[0046]
Specific examples of such organic sulfonic acid metal salts include sodium stearyl sulfonate, sodium octyl sulfonate, sodium dodecyl sulfonate, sodium stearyl benzene sulfonate, sodium octyl benzene sulfonate, sodium dodecyl benzene sulfonate, or carbon number. A preferable example is a mixture of sodium alkyl sulfonates having an average of 14 units.
[0047]
The amount of the organic sulfonic acid metal salt added to the polyester needs to be in the range of 0.05 to 10% by weight based on the fiber weight. When the blending amount is less than 0.05% by weight, the antistatic property of the polyester fiber obtained by melt spinning is not sufficient, and when it is more than 10% by weight, mixing operation, spinning, etc. become difficult, which is not preferable.
[0048]
Such polyoxyalkylene polyethers and organic sulfonic acid metal salt antistatic agents are added to the polyester at any stage prior to the completion of the spinning process. For example, it can be added to the raw material for polyester production in advance, or can be added at the time of the first polymerization reaction of the polyester polymerization or at the subsequent second polymerization reaction, and the polyester obtained after the polycondensation reaction For example, a method of melt-mixing the antistatic agent with a melt extruder, a method of adding to the polyester at a stage before the exit of the melt-molding machine, and the like can be employed. Further, the polyoxyalkylene polyether and the organic sulfonic acid metal salt may be added in separate steps.
In the present invention, the following formula (5)
X = N × W (5)
(In the above formula, N and W are the number of particles having a diameter of 2.5 μm or more observed when 20 mg of polyester is sandwiched between two preparations and melted at 285 ° C. under a load of 10 g to form a thin film having a diameter of 1 cm. (Pieces / cm²) And the amount of antistatic agent in the polyester composition (parts by weight relative to 100 parts by weight of the polyester). )
The dispersibility X of the antistatic agent represented by the formula is 0.1-1. Preferably they are 0.2 or more and 0.5 or less.
[0049]
When the dispersibility X defined by the above formula is less than 0.1, the antistatic agent is extremely finely dispersed, and the antistatic performance of the fiber obtained from such a composition is not preferable. . On the other hand, when the dispersibility exceeds 1.0, dispersion of the antistatic agent becomes insufficient, and the antistatic agent tends to ooze out on the chip surface or the fiber surface. For this reason, when the tip is melt-spun with an extruder, the tip is not properly bitten, and the antistatic performance of the fiber is reduced.
[0050]
When spinning a polyester blended with an antistatic agent, it is not necessary to employ special conditions, and any melt spinning conditions can be employed. In the production method of the present invention, the cross-sectional shape of the fiber can be arbitrarily selected as long as the effects of the present invention are exhibited, and may be appropriately selected, such as a round shape and an irregular shape, and the size of the cross section. There is no restriction on the fineness.
[0051]
Moreover, the polyester fiber obtained in the production method of the present invention may contain a catalyst, an anti-coloring agent, a heat-resistant agent, a fluorescent agent, a flame retardant, a dye, a pigment, inert fine particles, and the like as necessary.
[0052]
Furthermore, in order to finely adjust the color tone of the polyester obtained, a kind of organic blue pigment and inorganic blue pigment such as azo, triphenylmethane, quinoline, anthraquinone, phthalocyanine, etc. in the production stage of the polyester in the reaction system The color adjusting agent which consists of the above can be added. In the production method of the present invention, as a matter of course, it is not necessary to use an inorganic blue pigment containing cobalt or the like that lowers the thermal stability of the polyester as a color adjusting agent. It is preferable not to contain cobalt.
[0053]
The polyester obtained by the method of the present invention usually has an L value obtained from a hunter-type color difference meter of 80.0 or more and a b value in the range of -2.0 to 5.0. If the L value of the polyester is less than 80.0, the whiteness will be low, and a high whiteness molded product that can be used in practice may not be obtained. Further, when the b value is less than −2.0, the blueness of the polyester is increased. On the other hand, when the b value exceeds 5.0, the yellowness of the obtained polyester becomes strong, and thus practically useful molding. In some cases, it cannot be used for manufacturing. The L value of the polyester obtained by the method of the present invention is preferably 82 or more, particularly preferably 83 or more, and the preferable range of the b value is -1.0 to 4.5, particularly preferably 0.0 to 4. 0.
[0054]
The L value and b value of the polyester obtained by the method of the present invention are measured by the following method. That is, a polyester sample was melted at 290 ° C. under vacuum for 10 minutes, formed on an aluminum plate into a plate having a thickness of 3.0 ± 1.0 mm, and the plate was immediately cooled in ice water. The plate is dried at 160 ° C. for 1 hour and then subjected to a crystallization treatment. After that, the plate is placed on a white standard plate for color difference meter adjustment, and the color of the test plate surface is changed to a Hunter type color difference meter CR manufactured by Minolta. Measured using -200.
[0055]
The polyester of the present invention is substantially free of cobalt atoms derived from the color-regulating cobalt compound. Polyesters containing cobalt atoms have the drawbacks of low thermal stability and easy decomposition. Here, “substantially free” means that a cobalt compound is not used as a color adjusting agent or a polycondensation catalyst, and therefore the resulting polyester does not contain a cobalt atom derived from the cobalt compound. To do. Therefore, the polyester of the present invention may contain a cobalt atom derived from a cobalt compound added for purposes other than the color adjusting agent and the catalyst.
[0056]
The intrinsic viscosity of the polyester in the present invention may be selected as appropriate, but is preferably in the range of 0.55 to 1.0. When the intrinsic viscosity is within this range, melt molding is easy and the strength of the molded product is high. A more preferable range of the intrinsic viscosity is 0.60 to 0.90, and particularly preferably 0.62 to 0.80.
[0057]
【Example】
The present invention will be further described in the following examples, but the scope of the present invention is not limited by these examples. However, as described above, the intrinsic viscosity, hue, titanium content, dispersibility, deposit layer generated on the spinneret and antistatic durability were measured by the methods described below.
[0058]
1) Intrinsic viscosity:
The intrinsic viscosity of the polyester was determined from the viscosity value measured at 35 ° C. for the orthochlorophenol solution.
[0059]
2) Color tone (L value and b value):
A polyester sample was melted at 290 ° C. under vacuum for 10 minutes, formed into a plate having a thickness of 3.0 ± 1.0 mm on an aluminum plate, and immediately cooled in ice water. The plate was dried at 160 ° C. for 1 hour. After the crystallization treatment, the plate was placed on a white standard plate for color difference adjustment, and the Hunter L value and b value on the plate surface were measured using a Hunter type color difference meter CR-200 manufactured by Minolta. The L value indicates the lightness, and the larger the value, the higher the lightness, and the b value the greater the value, the greater the degree of yellowing.
[0060]
3) Titanium content of the catalyst:
The titanium concentration in the catalyst compound was measured using a fluorescent X-ray measuring device 3270 manufactured by Rigaku Corporation.
[0061]
4) Deposit layer generated in the spinneret:
Polyester is made into chips, which are melted at 290 ° C., discharged from a spinneret with a hole diameter of 0.15 mmφ and 12 holes, spun at 600 m / min for 2 days, The layer height was measured. As the height of the adhered layer increases, bending is more likely to occur in the filament flow of the discharged polyester melt, and the moldability of the polyester becomes lower. That is, the height of the deposit layer generated in the spinneret is an index of the moldability of the polyester.
[0062]
5) Antistatic durability:
The knitted fabric produced using the obtained polyester fiber was washed with a 0.3% aqueous solution of an anionic detergent (“Zab” manufactured by Kao Soap Co., Ltd.) at 40 ° C. for 30 minutes in an electric washing machine for home use. Thereafter, the knitted fabric was dried.
[0063]
The dried sample was immersed in water for 30 minutes or more, and then dehydrated for 5 minutes by a household electric washing machine dehydrator. The specific resistance value after the sample before and after washing was left standing at 25 ° C. and 65% relative humidity all day and night was measured.
[0064]
6) Dispersibility X of antistatic agent
The number of particles having a diameter of 2.5 μm or more (pieces / cm) observed when 20 mg of the obtained polyester is sandwiched between two preparations and melted at 285 ° C. under a load of 10 g to form a thin film having a diameter of 1 cm.²) And the amount of antistatic agent in the polyester composition (parts by weight relative to 100 parts by weight of the polyester).
[0065]
    [Reference example1]
  1) Preparation of catalyst (A):
  0.8 parts by weight of trimellitic anhydride is dissolved in 2.5 parts by weight of ethylene glycol, and 0.7 parts by weight of titanium tetrabutoxide (0.5 mol% based on the molar amount of trimellitic anhydride) is dropped into this solution. Then, this reaction system was kept at 80 ° C. for 60 minutes in air at normal pressure to react titanium tetrabutoxide with trimellitic anhydride, thereby aging the reaction product. Thereafter, the reaction system was cooled to room temperature, and 15 parts by weight of acetone was added thereto. It was filtered through 5 filter paper, collected, and dried at a temperature of 100 ° C. for 2 hours. The titanium content of the obtained reaction product (titanium compound (2)) was 11.2% by weight.
[0066]
Next, 3.6 parts by weight of phenylphosphonic acid was dissolved in 131 parts by weight of ethylene glycol by heating at 120 ° C. for 10 minutes. After further adding 40 parts by weight of ethylene glycol to 134.5 parts by weight of this ethylene glycol solution, 5.0 parts by weight of the titanium compound (2) was dissolved therein. The obtained reaction system was stirred at 120 ° C. for 60 minutes to react the titanium compound (2) with phenylphosphonic acid to obtain a white slurry of the catalyst (A) containing the reaction product. The titanium content of the catalyst (A) slurry was 0.3% by weight.
[0067]
2) Production of polyester:
166 parts by weight of terephthalic acid and 75 parts by weight of ethylene glycol are subjected to an esterification reaction at 240 ° C., and then the obtained reaction product is put into a polycondensation flask equipped with a rectifying column, and the catalyst (A) slurry as a polycondensation catalyst 0.95 parts by weight (based on the molar amount of terephthalic acid, 20 × 10 in terms of molar amount of titanium atom)^-3Mol%) and 0.0002 parts by weight of terazole blue as a color adjuster.
[0068]
  After heating at a temperature of 285 ° C. and normal pressure for 30 minutes, reacting at a temperature of 280 ° C. under atmospheric pressure for 30 minutes, then reacting under a reduced pressure of 4.0 kPa (30 mmHg) for 15 minutes, and then returning to atmospheric pressure once. The following chemical formula(7)
[0069]
Embedded image

[0070]
(However, j is an integer of 18 to 28 and average 21, P is 100 as an average value, and m is 5 as an average value.)
After adding 8 parts of a polyoxyethylene polyether represented by the following formula and 10 parts of a mixture of sodium alkyl sulfonate having 8 to 20 carbon atoms and an average carbon number of 14, the system was gradually depressurized and stirred. The reaction was performed for 80 minutes. The final internal temperature was 280 ° C., the final internal pressure was 42.7 Pa (0.32 mmHg), and the intrinsic viscosity of the obtained polyester was 0.650.
[0071]
After completion of the reaction, the polyester was chipped according to a conventional method and dried. The addition amounts of polyoxyethylene polyether and sodium alkyl sulfonate in the polyester were 2.5 wt% and 3 wt%, respectively, and the dispersibility X was 0.83. Next, using this dry-processed chip, a 333 dtex / 36 fil raw yarn was prepared according to a conventional method, and stretched 4.0 times to obtain an 83.25 dtex / 36 fil multifilament. Knitted fabric was obtained from this filament. The results are shown in Tables 1 and 2.
[0072]
    [Reference example2]
  1) Production of polyester:
  194 parts by weight of dimethyl terephthalate, 124 parts by weight of ethylene glycol and 0.12 parts by weight of calcium acetate are put into a reaction vessel equipped with a rectifying column, and transesterification is performed at 220 ° C., and the theoretical amount of methanol produced is distilled off. Thereafter, 0.09 part by weight of phosphoric acid was added to the reaction mixture to complete the first stage reaction. Next, the reaction mixture is put into a polycondensation flask equipped with a rectifying column, and this reaction mixture is used as a polycondensation catalyst.Reference example3.2 parts by weight of the catalyst (A) slurry obtained by the same method as 1 (based on the molar amount of dimethyl terephthalate, the content of titanium compound (2) is 20 × 10 in terms of molar amount of titanium atom)^-3Mol%), and 0.0002 parts by weight of terazole blue as a color adjuster.
[0073]
This reaction system was reacted at a temperature of 280 ° C. under atmospheric pressure for 30 minutes, then reacted at a reduced pressure of 4.0 kPa (30 mmHg) for 15 minutes, and then returned to atmospheric pressure, and expressed by the above formula (6). 8 parts of polyoxyethylene polyether and 10 parts of a mixture of alkyl sulfonic acid soda having 8 to 20 carbon atoms and an average carbon number of 14 are added, and the system is gradually depressurized and reacted for 80 minutes with stirring. I let you. The final internal temperature was 280 ° C., the final internal pressure was 42.7 Pa (0.32 mmHg), and the intrinsic viscosity of the obtained polyester was 0.651. After completion of the reaction, the polyester was chipped according to a conventional method and dried. The addition amounts of polyoxyethylene polyether and sodium alkyl sulfonate in the polyester were 2.5% by weight and 3% by weight, respectively, and the dispersibility X was 0.74. Next, using this dry-processed chip, a 333 dtex / 36 fil raw yarn was prepared according to a conventional method, and stretched 4.0 times to obtain an 83.25 dtex / 36 fil multifilament. The results are shown in Tables 1 and 2.
[0074]
    [Reference example3]
  1) Production of polyester:
  Reference example2 except that the polyoxyalkylene glycol-based polyether is changed to 8 parts of polyoxyethylene glycol having a molecular weight of 4000, and the organic sulfonic acid metal salt is changed to 9 parts of alkylsulfonic acid soda having 8 to 20 carbon atoms and an average carbon number of 12. Were similarly subjected to a polycondensation reaction to obtain polyester and fibers. The results are shown in Tables 1 and 2. The addition amounts of polyoxyethylene polyether and sodium alkyl sulfonate in the polyester were 2.5% by weight and 3% by weight, respectively.
[0075]
    [Example1-3]
  1) Production of polyester:
  Reference example1, a polycondensation reaction was carried out in the same manner except that the phosphorus compound was changed to the compounds and values shown in Table 1 to obtain polyesters and fibers. The results are shown in Tables 1 and 2. In these examples, the addition amounts of polyoxyethylene-based polyether and sodium alkyl sulfonate in the polyester were 2.5% by weight and 3% by weight, respectively.
[0076]
    [Comparative Example 1]
  Reference exampleA polyester was produced in the same manner as in the production method of polyester No. 2. However, only titanium tetrabutoxide was used as the polycondensation catalyst, and the addition amount of this catalyst was 20 × 10 in terms of molar amount of titanium based on the molar amount of dimethyl terephthalate.^-3The concentration and amount of catalyst slurry were adjusted so as to be%. The results are shown in Tables 1 and 2.
[0077]
[Comparative Example 2]
1) Preparation of catalyst (B):
0.80 part by weight of trimellitic anhydride is dissolved in ethanol, 0.64 part by weight of titanium tetrabutoxide is added dropwise to this solution, and the resulting reaction system is heated to a temperature of 80 ° C. under normal pressure in air. Holding for a minute, titanium tetrabutoxide and trimellitic anhydride were reacted to age. After the reaction ripening, the reaction system was cooled to room temperature, 15 parts by weight of acetone was added thereto, and the generated precipitate was collected by filtration. The titanium content of the catalyst (B) thus obtained was 11.3% by weight.
[0078]
  2) Production of polyester:
  Reference exampleA polyester was produced in the same manner as in the production method of polyester No. 2. However, the catalyst (B) is used as the polycondensation catalyst, and the amount of the catalyst (B) added is 20 × 10 in terms of molar amount of titanium atom based on the molar amount of dimethyl terephthalate.^-3The catalyst concentration and addition amount of the slurry were adjusted so as to be mol%. The results are shown in Tables 1 and 2.
[0079]
    [Comparative Example 3]
  Reference exampleA polyester was produced in the same manner as in the method for producing polyester No. 2. However, antimony trioxide was used as the polycondensation catalyst, and the addition amount of this catalyst was 25 × 10 in terms of molar amount of antimony atom based on the molar amount of dimethyl terephthalate.^-3The concentration of the slurry and the amount added were adjusted to be%. The results are shown in Tables 1 and 2.
[0080]
[Comparative Examples 4 to 6]
In Comparative Examples 1 to 3, the polyoxyalkylene glycol polyether is 8 parts of polyoxyethylene glycol having a molecular weight of 4000, and the organic sulfonic acid metal salt is 9 parts of alkylsulfonic acid soda having 8 to 20 carbon atoms and 12 carbon atoms in average. A polyester and fiber were obtained by performing a polycondensation reaction in the same manner except that the polyester and fiber were changed. The results are shown in Tables 1 and 2.
[0081]
[Table 1]

[0082]
[Table 2]

[0083]
【The invention's effect】
According to the polyester for antistatic fibers of the present invention, it is possible to provide a polyester having a good color tone (b value) and exhibiting excellent antistatic properties, and the polyester obtained by the method of the present invention is Even if spinning is performed continuously for a long time through the spinneret, the amount of the deposit on the die is very small, and it has excellent performance that it has excellent moldability.

Claims (4)

It consists of polyester with ethylene terephthalate as the main repeating unit,
A) As a catalyst at the time of polyester polymerization, the following formula (1)

(In the above formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ represent the same or different alkyl groups having 2 to 10 carbon atoms, and m represents an integer of 1 to 3).
And the following formula (2)

(In the above formula, _{R 2} represents an alkyl group or an aryl group having 6 to 20 carbon atoms, 2 to 18 carbon atoms.)
A titanium / phosphorus reaction product in which the phosphorus compound represented by the formula (1) is a composition in which the number of moles of phosphorus element relative to the number of moles of titanium element (P / Ti) is 1 to 4 in ethylene glycol, and The amount of titanium element contained in the polyester is in the range of 2 to 40 mmol% with respect to the total dicarboxylic acid residue component,
B) As an antistatic agent at any stage before the completion of the spinning process of the polyester, the following formula (3)

(In the above formula, Z represents an organic compound residue having 1 to 6 active hydrogens, R ₃ represents an alkylene group or substituted alkylene group having 6 or more carbon atoms, and R ₄ represents a hydrogen atom or 1 to 6 carbon atoms. 40 monovalent hydrocarbon group, monovalent hydroxy hydrocarbon group having 2 to 40 carbon atoms or monovalent acyl group having 2 to 40 carbon atoms, k is an integer of 1 to 6, and s is s ≧ (An integer satisfying 70 / k, t represents an integer of 1 or more.)
The polyoxyalkylene polyether represented by the formula: 0.2 to 30% by weight based on the weight of the polyester, and the following formula (4)
(R ₅ SO ₃ ) _r M (4)
(In the above formula, R ₅ represents an alkyl group having 3 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms which may be substituted with an alkyl group, M represents an alkali metal or an alkaline earth metal, and r represents 1 when M is an alkali metal, and 2 when M is an alkaline earth metal)
An organic sulfonic acid metal salt represented by the formula (1) is added so as to be 0.05 to 10% by weight based on the weight of the polyester,
C) The following formula (5)
X = N × W (5)
(In the above formula, N and W are the number of particles having a diameter of 2.5 μm or more observed when 20 mg of polyester is sandwiched between two preparations and melted at 285 ° C. under a load of 10 g to form a thin film having a diameter of 1 cm. (Pieces / cm ² ) and the amount of antistatic agent in the polyester composition (parts by weight relative to 100 parts by weight of polyester).
Dispersibility X of the antistatic agent represented by the formula is 0.1 to 1,
D) Polyester for antistatic fibers having an intrinsic viscosity of 0.55 or more. The formula (2) antistatic textile polyester according to claim 1, wherein the phosphorus compound is a monoalkyl phosphate. The polyester for antistatic fibers according to claim 1 or 2 , wherein the titanium compound of the formula (1) is a polyester production catalyst selected from titanium tetraalkoxides, octaalkyltrititanates, and hexaalkyldititanates. . The titanium compound of the above formula (1) is previously represented by the following formula (6)

(In the above formula, q represents an integer of 2 to 4.)
And reacting with the phosphorus compound of the above formula (2) after reacting with the polyhydric carboxylic acid and / or acid anhydride thereof at a composition in the reaction molar ratio (2: 1) to (2: 5) range. The polyester for antistatic fibers according to any one of claims 1 to 3 .