JP2004332186A - Nanoporous fiber - Google Patents

Abstract

An object of the present invention is to provide a nanoporous fiber in which, unlike conventional porous fibers, nanopores containing almost no coarse pores are uniformly dispersed.
The object is achieved by a nanoporous fiber having pores having a diameter of 100 nm or less, wherein the area ratio of pores having a diameter of 200 nm or more to the entire fiber cross section is 1.5% or less. You.
[Selection diagram] Fig. 1

Description

【００６７】

【００６８】

なお、共重合ＰＥＴは０．０５重量％の酸化チタンを含有していた。そして、このポリマーアロイを２７０℃の溶融部２で溶融し、紡糸温度２７５℃のスピンブロックに導いた。そして、限界濾過径１５μｍの金属不織布でポリマーアロイ溶融体を濾過した後、溶融紡糸した（図２３）。この時、溶融部２から吐出までの滞留時間は１０分間であった。口金としては図２４に示すように吐出孔上部に直径０．２ｍｍの計量部１１を備えた、吐出孔径１３が０．５ｍｍ、吐出孔長１２が１．２５ｍｍのものを用いた。そして、この時の単孔あたりの吐出量は２．１ｇ／分とし、ポリマーアロイの口金吐出線速度は１０ｍ／分であった。また、口金下面から冷却開始点（チムニー５の上端部）までの距離は９ｃｍであった。吐出された糸条は２０℃の冷却風で１ｍにわたって冷却固化され、口金４から１．８ｍ下方に設置した給油ガイド７で給油された後、非加熱の第１引き取りローラー８および第２引き取りローラー９を介して３８００ｍ／分で巻き取られた。この時の紡糸性は良好であり、２４時間の連続紡糸の間の糸切れはゼロであった。また、ナイロンで問題となる巻き取りパッケージの経時膨潤によるパッケージ崩れも無く、優れた取り扱い性であった。そして、これに図２７の装置を用い延伸仮撚り加工を施した。この時、延伸倍率は１．３倍、ヒーター２３温度は１６５℃、回転子２５としてはウレタンディスクの３軸ツイスターを用い、Ｄ／Ｙ比は１．６５とした。得られた５０ｄｔｅｘ、１２フィラメントの仮撚り加工糸は強度３．５ｃＮ／ｄｔｅｘ、伸度２９％、熱収縮率８％、ＣＲ３８％の優れた物性を示した（表２）。また、得られたポリマーアロイ捲縮糸の横断面をＴＥＭで観察したところ、Ｎ６が海（濃い部分）、共重合ＰＥＴが島（薄い部分）の海島構造を示し（図２）、島の平均直径は２５ｎｍであり、共重合ＰＥＴが超微分散化したポリマーアロイ繊維が得られた。直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．９％であった。ここで、島全体に対する面積比とは島成分の面積の総和に対する比率のことを言い、粗大な凝集ポリマーの目安となるものである。また、繊維縦断面ＴＥＭ観察から島は筋状構造を形成していることが分かった。
【００６９】
このポリマーアロイ捲縮糸Ｓ撚り／Ｚ撚り双糸として丸編みを作製し、これを３％の水酸化ナトリウム水溶液（９０℃、浴比１：１００）で１時間浸漬することでポリマーアロイ繊維中の共重合ＰＥＴの９９％以上を加水分解除去した。その後、水洗し、乾燥した。これによりＮ６ナノポーラスファイバーからなる丸編みを得た。
【００７０】
このＮ６ナノポーラスファイバーの繊維横断面をＴＥＭで観察した（図１）ところ、直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は２５ｎｍであった。ここで、濃い部分がＮ６ポリマー、薄い部分が細孔に相当するが、細孔は独立孔であることがわかった。
【００７１】
また、このＮ６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。さらにこれの吸湿率（ΔＭＲ）を測定したところ、５．６％と綿を凌駕する優れた吸湿性を示した。また、これは可逆的な水膨潤性を示し、このＮ６ナノポーラスファイバーからなる丸編みを１８０℃で１分間セットしたものから抜き出した糸の糸長手方向の膨潤率は７％であった。さらに、これの力学特性を測定したところ、強度２．６ｃＮ／ｄｔｅｘ、伸度３０％であり、繊維製品として充分な力学特性を示した。Ｎ６ナノポーラスファイバーの物性は表１に示した。
【００７２】
実施例２
Ｎ６を溶融粘度１２６０ｐｏｉｓｅ（２８０℃、剪断速度２４３２ｓｅｃ^−１）のＮ６を用い溶融粘度比を表２記載のように変更して実施例１と同様に溶融紡糸、延伸仮撚りを行った。この時、単孔あたりの吐出量、口金孔数を変更し１０５ｄｔｅｘ、９６フィラメント、強度３．８ｃＮ／ｄｔｅｘ、伸度２９％、熱収縮率８％、ＣＲ３５％のポリマーアロイ捲縮糸を得た（表２）。得られたポリマーアロイ捲縮糸の繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造を形成していることが分かった。
【００７３】
このポリマーアロイ捲縮糸Ｓ撚り／Ｚ撚り双糸として実施例１と同様に丸編み後、アルカリ処理により共重合ＰＥＴの９９％以上を除去し、Ｎ６ナノポーラスファイバーからなる丸編みを得た。
【００７４】
このＮ６ナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果、島ポリマーが抜けた跡の細孔の平均直径は２０ｎｍであり、直径が５０ｎｍ以上の大きな細孔は皆無であった。これらの細孔は独立孔であった。
【００７５】
また、このＮ６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。Ｎ６ナノポーラスファイバーは表１に示すように優れた物性であった。
【００７６】
実施例３
実施例１で得たポリマアロイチップを用い、吐出量と口金孔数を変更し、紡糸速度を９００ｍ／分として実施例１と同様に溶融紡糸を行った。この時の溶融部２から吐出までの滞留時間は１２分間であった。紡糸性は良好であり、２４時間の連続紡糸の間の糸切れはゼロであった。また、ナイロンで問題となる巻き取りパッケージの経時膨潤によるパッケージ崩れも無く、優れた取り扱い性であった。そして、これを第１ホットローラー１６の温度を７０℃、第２ホットローラー１７の温度を１３０℃として延伸熱処理した（図２５）。この時、第１ホットローラー１６と第２ホットローラー１７間の延伸倍率を３．２倍とした。得られたポリマーアロイ繊維は７０ｄｔｅｘ、３４フィラメント、強度３．７ｃＮ／ｄｔｅｘ、伸度４７％、Ｕ％＝１．２％、熱収縮率１１％の優れた特性を示した。また、得られたポリマーアロイ繊維の横断面をＴＥＭで観察したところ、Ｎ６が海（濃い部分）、共重合ＰＥＴが島（薄い部分）の海島構造を示し（図３）、島の平均直径は３８ｎｍであり、共重合ＰＥＴが超微分散化したポリマーアロイ繊維が得られた。また、直径２００ｎｍ以上の島は島全体に対して面積比で１．２％であった。なお、溶融混練したポリマーアロイチップの断面ＴＥＭ写真を図７に示すが、島ポリマーが粒径２０〜３０ｎｍまで超微分散化しており、繊維横断面での島ポリマー直径（図３）同等以下であった。口金吐出から延伸を通じてポリマーは５００倍程度に引き延ばされ、本来、繊維横断面中では島ポリマー直径はポリマーアロイ中に比べ１／２２以下にならなければならいにもかかわらず、繊維横断面での島ポリマー直径の方が大きいということは、ポリマーアロイの溶融から口金吐出されるまでに島ポリマーが再凝集したことを示しており、これを抑制しながら島ポリマーを超微分散させるためには本実施例のように紡糸条件を適切に選ぶことが重要であることがわかる。ポリマーアロイ繊維の物性は表２に示した。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。
【００７７】
ここで得られたポリマーアロイ繊維を用いて丸編みを作製し、これを３％の水酸化ナトリウム水溶液（９０℃、浴比１：１００）で１時間浸漬することでポリマーアロイ繊維中の共重合ＰＥＴの９９％以上を加水分解除去した。その後、水洗し、乾燥した。
【００７８】
このＮ６ナノポーラスファイバーを光学顕微鏡で繊維側面観察を行ったところ、アルカリ処理前の繊維に比べ繊維径が若干減少しており、島ポリマーを除去することによって繊維半径方向に収縮が起こっていることが分かった。次に、これの繊維側面をＳＥＭにより観察したところ、倍率２０００倍程度では繊維表面に凹凸は見られずきれいな表面形態であった。また、このＮ６ナノポーラスファイバーの繊維横断面をＴＥＭで観察した（図５）ところ、金属染色による濃淡斑が元のポリマーアロイ繊維（図３）よりも微細になっていた。ここで、濃い部分はＮ６高密度部分、淡い部分はＮ６低密度部分である。そして淡い部分が細孔に相当すると考えられる。すなわち、島ポリマー除去により細孔サイズは元の島ポリマーよりも微細化し、細孔の平均直径は１５ｎｍであり、直径が５０ｎｍ以上の粗大細孔は皆無であった。また、繊維縦断面を観察したところ、元のポリマーアロイでは共重合ＰＥＴが筋状に伸びていた（図４）のに対し、Ｎ６ナノポーラスファイバーでは粒状の淡い部分が観察された（図６）。図５および図６の濃淡パターンから、これらの細孔は独立孔であると判断した。
【００７９】
また、このＮ６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。さらにこれの吸湿率（ΔＭＲ）を測定したところ、６％と綿を凌駕する優れた吸湿性を示した。また、このＮ６ナノポーラスファイバーの力学特性を測定したところ、強度２．０ｃＮ／ｄｔｅｘ、伸度７０％であり、繊維製品として充分な力学特性を示した。また、これは可逆的な水膨潤性を示し、このＮ６ナノポーラスファイバーからなる丸編みを１８０℃で１分間セットしたものから抜き出した糸の糸長手方向の膨潤率は７％であった。Ｎ６ナノポーラスファイバーの物性は表１に示した。
【００８０】
実施例４、５
Ｎ６を溶融粘度１２６０ｐｏｉｓｅまたは１５４０ｐｏｉｓｅ（２８０℃、剪断速度２４３２ｓｅｃ^−１）の実施例３で用いたものよりも高粘度のＮ６を用い、Ｎ６と共重合ＰＥＴの溶融粘度比を表２記載のように変更して実施例３と同様に溶融紡糸、延伸・熱処理を行った。この時、単孔あたりの吐出量、口金孔数を変更し１０５ｄｔｅｘ、９６フィラメントのポリマーアロイ繊維を得た。紡糸性はいずれも良好であり、２４時間の連続紡糸の間の糸切れはゼロであった。得られたポリマーアロイ繊維は、いずれも粗大な凝集ポリマー粒子を含まず、直径２００ｎｍ以上の島は島全体に対し面積比で０．１％以下、直径１００ｎｍ以上の島も面積比で０．１％以下であった。また、糸物性は表２に示すとおり優れたものであった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。
【００８１】
これらのポリマーアロイ繊維を実施例３と同様に丸編み後、アルカリ処理により共重合ＰＥＴの９９％以上を除去し、Ｎ６ナノポーラスファイバーからなる丸編みを得た。
【００８２】
このＮ６ナノポーラスファイバーを光学顕微鏡、ＳＥＭで観察したところ実施例３同様に島ポリマー除去により繊維半径方向に収縮が起こり、倍率２０００倍程度では繊維表面に凹凸は見られずきれいな表面形態であった。また、このＮ６ナノポーラスファイバーの繊維横断面をＴＥＭで観察したところ、金属染色による濃淡斑が元のポリマーアロイ繊維よりも微細になり、島ポリマー除去により細孔サイズは元の島ポリマーよりも微細化し、細孔の平均直径は１５ｎｍであり、直径が５０ｎｍ以上の大きな細孔は皆無であった。また、繊維縦断面を観察したところ、粒状の濃淡がシリンダー状に並んだパターンとなっていた。以上のＴＥＭ観察から、これらの細孔は独立孔と判断した。
【００８３】
また、このＮ６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。Ｎ６ナノポーラスファイバーは表１に示すように優れた物性であった。
【００８４】
実施例６
Ｎ６と共重合ＰＥＴブレンド比を５０重量％／５０重量％とし、単孔あたりの吐出量、口金孔数を変更して実施例３と同様に溶融紡糸、延伸・熱処理を行い、９０ｄｔｅｘ、３４フィラメントのポリマーアロイ繊維を得た。紡糸性は良好であり、２４時間の連続紡糸の間の糸切れはゼロであった。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察結果を図８に示すが、共重合ＰＥＴは直径１０ｎｍ程度の島が数珠状に繋がり、短軸１０ｎｍ以下、長軸５０〜８０ｎｍ程度の層状の島として存在しており、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。また、糸物性は表２に示すとおり優れたものであった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。
【００８５】
このポリマーアロイ繊維を実施例３と同様に丸編み後、アルカリ処理により共重合ＰＥＴの９９％以上を除去し、Ｎ６ナノポーラスファイバーからなる丸編みを得た。
【００８６】
このＮ６ナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果を図９に示すが、細孔の平均直径は２０ｎｍであり、直径が５０ｎｍ以上の大きな細孔は皆無であった。図９からこれらの細孔は独立孔であることがわかった。
【００８７】
また、このＮ６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。Ｎ６ナノポーラスファイバーは表１に示すように優れた物性であった。
【００８８】
実施例７
実施例３で用いたＮ６（５０重量％）と５−ナトリウムスルホイソフタル酸を１２ｍｏｌ％、イソフタル酸を２６ｍｏｌ％共重合したＰＥＴ（５０重量％）とを２軸押し出し混練機で２４５℃で混練し、ポリマーアロイチップを得た。このポリマーアロイを紡糸温度２５０℃で溶融し、口金孔径０．６ｍｍとし、単孔あたりの吐出量を変更して実施例３と同様に溶融紡糸を行い、紡糸速度８００ｍ／分で未延伸糸を巻き取った。これを延伸倍率３．４倍、第１ホットローラー温度９０℃、第２ホットローラー温度１３０℃で延伸熱処理した。これにより、８５ｄｔｅｘ、３６フィラメントのポリマーアロイ糸を得た。紡糸性は良好であり、２４時間の連続紡糸の間の糸切れはゼロであった。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察結果を図１０に示すが、共重合ＰＥＴは短軸１０〜３０ｎｍ、長軸５０〜１００ｎｍ程度の層状の島として存在しており、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。また、糸物性は表２に示すとおり優れたものであった。
【００８９】
このポリマーアロイ繊維を実施例３と同様に丸編み後、３重量％の水酸化ナトリウム水溶液（９０℃、浴比１：５０）で１時間処理することにより、共重合ＰＥＴの９９％以上を溶解除去し、Ｎ６ナノポーラスファイバーからなる丸編みを得た。この時、顕著な繊維の半径方向への収縮が観察された（半径収縮率は約２２％、横断面積収縮率は約４０％）。この溶解除去後のナイロン６糸の繊維側面をＳＥＭで観察（２０００倍）したが、共重合ＰＥＴが抜けた跡であるいわゆる筋状溝やボイドは観察できなかった。
【００９０】
このＮ６ナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果を図１１に示すが、細孔の平均直径は１０ｎｍであり、直径が５０ｎｍ以上の大きな細孔は皆無であった。
【００９１】
また、このＮ６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。さらに、Ｎ６ナノポーラスファイバーの水による膨潤性を測定したところ、糸長手方向の膨潤率は１１．１％と大きな値を示した。また、３回目の測定でも糸長手方向の膨潤率の低下はほとんど無く、可逆性・耐久性とも充分であった。また、この丸編みを１４０℃で３０分間熱処理後、Ｎ６ナノポーラスファイバーの水による膨潤性を測定したところ、糸長手方向の膨潤率は７．３％と熱処理前に比べると膨潤率は低下したが、なお通常Ｎ６繊維の３％に比べるとはるかに大きな値であった。このことは熱処理により糸長手方向の膨潤率を制御できることを示しており、布帛設計し易いというメリットとなる。Ｎ６ナノポーラスファイバーは表１に示すように優れた物性であった。
【００９２】
実施例８
共重合ＰＥＴをイソフタル酸を７ｍｏｌ％、ビスフェノールＡエチレンオキサイド付加物を４ｍｏｌ％共重合したＰＥＴ（融点２２５℃、０．０５重量％の酸化チタンを含有）として、Ｎ６と共重合ＰＥＴの重量比を５０重量％／５０重量％、口金孔径を０．７ｍｍとして実施例３と同様にして溶融紡糸、延伸・熱処理を行った。問題となるほどではないが実施例３に比べると紡糸が不安定化し、２４時間の連続紡糸の間の糸切れは２回であった。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察結果を図１２に示すが、粗大な凝集ポリマー粒子はわずかであったが、島の平均直径が１４３ｎｍ、直径が２００ｎｍ以上の島の島全体に対する面積比は５％であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。糸物性は表２に示した。
【００９３】
このポリマーアロイ繊維を実施例３と同様に丸編み後、アルカリ処理により共重合ＰＥＴの９９％以上を除去し、Ｎ６ナノポーラスファイバーからなる丸編みを得た。
【００９４】
このＮ６ナノポーラスファイバーを光学顕微鏡で観察したところ実施例１同様に島ポリマー除去により繊維半径方向に収縮が見られた。また、このＮ６ナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果を図１３に示すが、島ポリマーが抜けた跡が潰れ幅１０〜３０ｎｍ、長さ１００ｎｍ程度の細孔となっており、直径が５０〜１００ｎｍの大きな細孔も散見された。しかし、直径２００ｎｍ以上の粗大細孔の面積比は０．５％であった。これの発色性評価を行ったが、実施例３に比べると発色性に劣るものの衣料用として使用可能なレベルであった。なお、これの細孔は独立孔であった。
【００９５】
実施例９
共重合ＰＥＴの代わりにポリアルキレンオキサイド誘導体の熱水可溶性ポリマーである第一工業製薬株式会社製“パオゲンＰＰ−１５”とし、単孔あたりの吐出量と口金孔数を変更、紡糸速度を４０００ｍ／分、延伸倍率を１．２倍として、実施例３と同様に溶融紡糸、延伸・熱処理を行い５５ｄｔｅｘ、６８フィラメントのポリマーアロイ繊維を得た。紡糸性は良好であり、２４時間の連続紡糸の間の糸切れはゼロであった。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は１．３％であった。また、糸物性は表２に示すとおり優れたものであった。
【００９６】
このポリマーアロイ繊維を実施例３と同様に丸編み後、１００℃の熱水で２時間処理することにより熱水可溶性ポリマーの９９％以上を除去し、Ｎ６ナノポーラスファイバーからなる丸編みを得た。
【００９７】
このＮ６ナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果、細孔の平均直径は３０ｎｍであり、直径が５０ｎｍ以上の大きな細孔は皆無であった。なお、これの細孔は独立孔であった。
【００９８】
また、このＮ６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。Ｎ６ナノポーラスファイバーは表１に示すように優れた物性であった。
【００９９】
実施例１０
共重合ＰＥＴの代わりに重量平均分子量１５万、溶融粘度８５７ｐｏｉｓｅ（２４０℃、２４３２ｓｅｃ^−１）、融点１７０℃のポリＬ乳酸（光学純度９９．５％以上）を用い混練温度を２２０℃として実施例１と同様に溶融混練した。なお、ポリ乳酸の重量平均分子量は以下のようにして求めた。試料のクロロホルム溶液にＴＨＦ（テトロヒドロフラン）を混合し測定溶液とした。これをＷａｔｅｒｓ社製ゲルパーミテーションクロマトグラフィー（ＧＰＣ）Ｗａｔｅｒｓ２６９０を用いて２５℃で測定し、ポリスチレン換算で重量平均分子量を求めた。なお、実施例１で用いたＮ６の２４０℃、２４３２ｓｅｃ^−１）での溶融粘度は５７０ｐｏｉｓｅであった。そして、単孔あたりの吐出量と口金孔数を変更、紡糸速度を３５００ｍ／分として、実施例１と同様に溶融紡糸を行い１０５ｄｔｅｘ、３６フィラメント、強度３．１ｃＮ／ｄｔｅｘ、伸度１０７％、Ｕ％１．２％の高配向未延伸糸を得た。紡糸性は良好であり、２４時間の連続紡糸の間の糸切れはゼロであった。これに延伸倍率を１．４倍として実施例１と同様に延伸仮撚り加工を施し、７６ｄｔｅｘ、３６フィラメント、強度４．０ｃＮ／ｄｔｅｘ、伸度２９％、Ｕ％１．３％、ＣＲ３５％の仮撚り加工糸を得た。この時、ポリＬ乳酸の融点を考慮し、ヒーター温度を１６０℃としたため、未解撚がほとんど無い品位にも優れた仮撚り加工糸が得られ、延伸仮撚りでの工程通過性も良好であった。得られたポリマーアロイ捲縮糸の繊維横断面をＴＥＭで観察結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島ポリマーの島成分全体に対する面積比は０．１％以下、島ポリマーの平均直径は８０ｎｍであった。また、糸物性は表１に示すとおり優れたものであった。
【０１００】
このポリマーアロイ捲縮糸を実施例１と同様に丸編み後、アルカリ処理することによりポリＬ乳酸の９９％以上を除去し、Ｎ６ナノポーラスファイバーからなる丸編みを得た。また、このＮ６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。
【０１０１】
この丸編みからＮ６ナノポーラスファイバーを引き出し、繊維横断面をＴＥＭで観察した結果、島ポリマーが抜けた跡は直径３０ｎｍ程度の細孔となっており、直径が５０ｎｍ以上の大きな細孔は皆無であった。また、得られたナノポーラスファイバーの強度は実施例１に比べても高いものであった。これは、実施例１で用いた共重合ＰＥＴに含まれるスルホン酸基が疑似架橋構造を生成し、Ｎ６の繊維構造形成を阻害する傾向があるのに対し、ＰＬＡはそのような悪影響が少ないためと考えられる。
【０１０２】
実施例１１
実施例３で用いたＮ６と共重合ＰＥＴを図２６の装置を用いてそれぞれ２７０℃、２９０℃で溶融した後、パック３内に設置した静止混練器２０（東レエンジニアリング社製“ハイミキサー”１０段）により１０４万分割して混合した。そして、これを絶対濾過径２０μｍの金属不織布フィルターで濾過した後、孔径０．３５ｍｍの口金孔から吐出した。この時、紡糸温度は２８０℃、口金４からチムニー５の上端までの距離は７ｃｍとした。これを紡糸速度９００ｍ／分で引き取り、第２引き取りローラー９を介して巻き取った。２４時間の紡糸を行ったが、紡糸での糸切れは皆無であり、良好な紡糸性を示した。これを図２５の装置を用いて延伸・熱処理した。この時、延伸倍率は３．２倍、第１ホットローラー１６温度は７０℃、第２ホットローラー１７温度は１３０℃とした。延伸・熱処理での糸切れは皆無であり、良好な延伸性を示した。
【０１０３】
これにより５６ｄｔｅｘ、１２フィラメントのポリマーアロイ繊維を得たが、Ｕ％は１．５％と充分糸斑の小さなものであった。また、これの繊維横断面をＴＥＭで観察したところ、金属染色により濃く染まったＮ６部分と淡いＰＥＴ部分が特殊な層構造を形成しており、ＰＥＴ層部分の厚みは概ね２０ｎｍ程度であった（図１４）。また、この繊維は繊維表層から１５０ｎｍ程度までは特殊な層構造が崩れ海島構造となっていたが、特殊な層構造部分の面積を見積もったところ、繊維横断面全体に対して９８％であり、繊維断面のほとんどが特殊な層構造を形成していた（図１５）。また、このポリマーアロイ繊維の縦断面をＴＥＭで観察したところ層が筋状になっていた（図１６）。
【０１０４】
このポリマーアロイ繊維を用いて丸編みを作製したが、製編工程でのトラブルは皆無であり、良好な工程通過性を示した。さらにこの丸編みを９５℃の３％水酸化ナトリウム水溶液に１時間浸漬し、ポリマーアロイ繊維からＰＥＴを完全に除去し、Ｎ６ナノポーラスファイバーからなる丸編みを得た。この丸編みはΔＭＲ＝５．７％と綿を凌駕する優れた吸湿性を示した。このナノポーラスファイバーの繊維横断面をＴＥＭで観察した（図１７）ところ、金属染色による濃淡斑が元のポリマーアロイ繊維よりも微細になっていた。ここで、濃い部分はＮ６高密度部分、淡い部分はＮ６低密度部分である。そして淡い部分が細孔に相当すると考えられる。また、繊維縦断面を観察したところ、元のポリマーアロイではＰＥＴが筋状に伸びていた（図１６）のに対し、ナノポーラスファイバーでは粒状の淡い部分が観察され（図１８）、細孔が潰れていることが示唆された。直径が５０ｎｍ以上の大きな細孔は皆無であった。
【０１０５】
また、このＮ６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。Ｎ６ナノポーラスファイバーは表１に示すように優れた物性であった。
【０１０６】
実施例１２
Ｎ６／共重合ＰＥＴブレンド比を５０重量％／５０重量％として実施例と同様に溶融紡糸を行った。紡糸性は良好であり、２４時間の紡糸で糸切れはゼロであった。これを図２５の装置を用いて延伸・熱処理した。この時、延伸倍率は３．２倍、第１ホットローラー１６温度は７０℃、第２ホットローラー１７温度は１３０℃とした。延伸・熱処理での糸切れは皆無であり、良好な延伸性を示した。
【０１０７】
得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察結果を図１９に示すが、共重合ＰＥＴは直径１０〜２０ｎｍ程度の微細な島が連結した数珠状島として存在しており、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。また、糸物性は表２に示すとおり優れたものであった。
【０１０８】
このポリマーアロイ繊維を実施例３と同様に丸編み後、アルカリ処理により共重合ＰＥＴの９９％以上を除去し、Ｎ６ナノポーラスファイバーからなる丸編みを得た。
【０１０９】
このＮ６ナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果を図２０に示すが、１０〜２０ｎｍ程度の微細な濃淡パターンを示し、直径２０ｎｍ以下の細孔が多数存在することが示唆された。また、直径が５０ｎｍ以上の大きな細孔は皆無であった。
【０１１０】
また、このＮ６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。Ｎ６ナノポーラスファイバーは表１に示すように優れた物性であった。
【０１１１】
実施例１３
Ｎ６をＮ６６として実施例１２と同様に溶融紡糸、延伸・熱処理を行った。この時、紡糸温度は２８０℃、Ｎ６６／共重合ＰＥＴのブレンド比は８０重量％／２０重量％とした。紡糸性は良好であり、２４時間の連続紡糸の間の糸切れはゼロであった。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。また、糸物性は表２に示すとおり優れたものであった。
【０１１２】
このポリマーアロイ繊維を実施例３と同様に丸編み後、アルカリ処理することにより共重合ＰＥＴの９９％以上を除去し、Ｎ６ナノポーラスファイバーからなる丸編みを得た。
【０１１３】
このＮ６６ナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果、細孔の平均直径は２０ｎｍとなっており、直径が５０ｎｍ以上の大きな細孔は皆無であった。
【０１１４】
また、このＮ６６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。Ｎ６６ナノポーラスファイバーは表１に示すように優れた物性であった。
【０１１５】
実施例１４
実施例１と同様に溶融紡糸を行い、図２８の装置を用いて紡糸直接延伸を行った。この時、単孔あたりの吐出量と口金孔数を変更し、第１ホットローラー２８の周速２０００ｍ／分、温度４０℃、第２ホットローラー２９の周速４５００ｍ／分、温度１５０℃として５５ｄｔｅｘ、１２フィラメント、強度４．４ｃＮ／ｄｔｅｘ、伸度３７％、Ｕ％１．２％、熱収縮率１２％のポリマーアロイ繊維を得た。紡糸性は良好であり、２４時間の紡糸で糸切れはゼロであった。得られたポリマーアロイ繊維は、いずれも粗大な凝集ポリマー粒子を含まず、直径２００ｎｍ以上の島は島全体に対し面積比で０．１％以下、直径１００ｎｍ以上の島も面積比で０．１％以下であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。また、糸物性は表２に示すとおり優れたものであった。
【０１１６】
これらのポリマーアロイ繊維を実施例３と同様に丸編み後、アルカリ処理により共重合ＰＥＴの９９％以上を除去し、Ｎ６ナノポーラスファイバーからなる丸編みを得た。
【０１１７】
このＮ６ナノポーラスファイバーの繊維横断面をＴＥＭで観察したところ、金属染色による濃淡斑が元のポリマーアロイ繊維よりも微細になり、島ポリマー除去により細孔サイズは元の島ポリマーよりも微細化し、直径が５０ｎｍ以上の大きな細孔は皆無であった。ＴＥＭ観察からこれの細孔は独立孔であると判断した。 また、このＮ６ナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。Ｎ６ナノポーラスファイバーは表１に示すように優れた物性であった。
【０１１８】
比較例１
混練方法を二軸押出混練機ではなく単純なチップブレンドとして図２３の装置を用い、実施例３と同様に溶融紡糸を行った。紡糸中のポリマーの吐出が安定せず、紡糸性は劣悪であり紡糸中に糸切れが頻発し、安定して糸を巻き取ることができなかった。しかし、わずかに得た未延伸糸を用いて実施例３同様に延伸・熱処理を行いポリマーアロイ繊維を得た。得られたポリマーアロイ繊維の横断面をＴＥＭで観察したところ、ブレンド斑が大きく、粗大な凝集ポリマー粒子が散見され、直径が２００ｎｍ以上の島の島全体に対する面積比は１０％であった。これを用いて実施例３同様にＮ６多孔繊維を得たが、直径２００ｎｍ以上の粗大細孔の面積比が２．０％と大きいため、散乱光が多く白っぽいものであり、発色性に劣るものであった。
【０１１９】
比較例２
実施例４で用いたＮ６を５０重量％と５−ナトリウムスルホイソフタル酸を２．５ｍｏｌ％、ビスフェノールＡエチレンオキサイド付加物３．５ｍｏｌ％共重合したポリエチレンテレフタレートを５０重量％を単純にチップブレンドした後、２９０℃で溶融し、孔径０．６ｍｍの丸孔口金から吐出し、図２３の装置を用い、紡糸速度１２００ｍ／分で溶融紡糸を行った。しかし、紡糸中のポリマーの吐出が安定せず、紡糸性は劣悪であり紡糸中に糸切れが頻発し、安定して糸を巻き取ることができなかった。わずかに得た未延伸糸を用いて１２０℃の熱プレートを用い延伸倍率２．７倍で延伸した。これにより、８５ｄｔｅｘ、２４フィラメントのポリマーアロイ繊維を得た。これの横断面をＴＥＭで観察したところ、ブレンド斑が大きく、粗大な凝集ポリマー粒子が散見され、直径が２００ｎｍ以上の島の島全体に対する面積比は１０％であった。
【０１２０】
そして、アルカリ処理により、これから共重合ＰＥＴの９９％以上を溶解除去した。この時に繊維径はほとんど変化しなかった。これの発色性評価を行ったが、直径２００ｎｍ以上の粗大細孔の面積比が５．０％と大きいため、散乱光が多く白っぽいものであり、発色性に劣るものであった。
【０１２１】
比較例３
実施例４で用いたＮ６を７０重量％、極限粘度０．６０の５−ナトリウムスルホイソフタル酸を４．５ｍｏｌ％、分子量４０００のポリエチレングリコールを８．５重量％共重合したポリエチレンテレフタレートを３０重量％を単純にチップブレンドして２８０℃で溶融し、孔径０．６ｍｍの丸孔口金から吐出し、図２３の装置を用い、紡糸速度１０００ｍ／分で溶融紡糸を行った。しかし、紡糸中のポリマーの吐出が安定せず、紡糸性は劣悪であり紡糸中に糸切れが頻発し、安定して糸を巻き取ることができなかった。わずかに得た未延伸糸を用いて延伸倍率３．３５倍、第１ホットローラー１６温度９０℃、第２ホットローラー１７温度１３０℃で延伸・熱処理した。これにより、８５ｄｔｅｘ、２４フィラメントのポリマーアロイ繊維を得た。これの横断面をＴＥＭで観察したところ、ブレンド斑が大きく、粗大な凝集ポリマー粒子が散見され、直径が２００ｎｍ以上の島の島全体に対する面積比は８％であった。
【０１２２】
そして、アルカリ処理により、これから共重合ＰＥＴの９０％以上を溶解除去した。この時に繊維径はほとんど変化しなかった。これの発色性評価を行ったが、直径２００ｎｍ以上の粗大細孔の面積比が２．４％と大きいため、散乱光が多く白っぽいものであり、発色性に劣るものであった。
【０１２３】
比較例４
実施例４で用いたＮ６を７７重量％、ホモＰＥＴを２０重量％、相溶化剤としてブロックポリエーテルポリアミド（ポリエチレングリコール部分４５重量％＋ポリ−ε−カプロラクタム部分５５重量％）を３重量％を単純にチップブレンドして図２３の装置を用い、実施例１と同様に溶融紡糸を行った。しかし、紡糸中のポリマーの吐出が安定せず、紡糸性は劣悪であり紡糸中に糸切れが頻発し、安定して糸を巻き取ることができなかった。わずかに得た未延伸糸を用いて実施例１と同様に延伸・熱処理した。これにより、７７ｄｔｅｘ、２４フィラメントのポリマーアロイ繊維を得た。これの横断面をＴＥＭで観察したところ、ブレンド斑が大きく、粗大な凝集ポリマー粒子が散見され、直径が２００ｎｍ以上の島の島全体に対する面積比は１４％であった。
【０１２４】
そして、アルカリ処理により、ＰＥＴの９９％以上を溶解除去した。この時に、実施例３とは異なり繊維径はほとんど変化しなかった。これの発色性評価を行ったが、直径２００ｎｍ以上の粗大細孔の面積比が４．６％と大きいため、散乱光が多く白っぽいものであり、発色性に劣るものであった。
【０１２５】
比較例５
Ｎ６／共重合ＰＥＴブレンド比を２５重量％／７５重量％として比較例３と同様に溶融紡糸を行った。しかし、紡糸中のポリマーの吐出が安定せず、紡糸性は劣悪であり紡糸中に糸切れが頻発し、安定して糸を巻き取ることができなかった。わずかに得た未延伸糸を用いて１２０℃の熱プレートを用い延伸倍率２．７倍で延伸した。これにより、８５ｄｔｅｘ、２４フィラメントのポリマーアロイ繊維を得た。これの横断面をＴＥＭで観察したところ、比較例１とは異なりアルカリ難溶解性のＮ６が島、アルカリ易溶解性の共重合ＰＥＴが海を形成していた。また、ブレンド斑が大きく、粗大な凝集ポリマー粒子が散見され、直径が２００ｎｍ以上の島の島全体に対する面積比は１０％であった。
【０１２６】
これを実施例１同様にアルカリ処理を施し、海共重合ＰＥＴを除去したところ、Ｎ６極細繊維が強固に接着した繊維が得られた。しかし、この繊維は強度を測定することも困難であり、実用的な繊維として取り扱うことは困難であった。
【０１２７】
次に、ポリマーアロイ繊維をギ酸で処理し島Ｎ６を溶解除去したが、同時に共重合ＰＥＴの脆化も著しく、ぼろぼろと崩れやすい物であり実用的な繊維として取り扱うことは困難であった。このようにこのポリマーアロイ繊維は実質的に多孔繊維を得ることができず、本発明の目的を達成できない物であった。
【０１２８】
参考例１
ＰＥＴにエチレンナフタレートを全酸成分に対し１０ｍｏｌ％共重合した共重合ＰＥＴ（極限粘度０．６０）とポリエーテルイミド（ゼネラルエレクトリック社製”ウルテム”−１０００）を共重合した共重合ＰＥＴが７０重量％になるように３０ｍｍφの二軸押し出し混練機を用い、３２０℃で混練した。ここで得られたポリマーアロイチップを十分乾燥後、口金孔数６ホール、単孔吐出量０．６ｇ／分、紡糸温度３１５℃、紡糸速度５００ｍ／分で溶融紡糸した。海ポリマーである共重合ＰＥＴの融点に比べ紡糸温度が高すぎたため紡糸が不安定化し、１２時間の紡糸で１０回の糸切れと紡糸性は不良であった。わずかに得られた未延伸糸を用いて、予熱ローラー温度９０℃、ホットプレート温度１２０℃、延伸倍率３．０倍で延伸を行ったが、糸切れが頻発した。ここで得られた延伸糸の強度は１．３ｃＮ／ｄｔｅｘと低いものであった。これは、混練温度、紡糸温度がメジャー成分である共重合ＰＥＴにとって高すぎたため熱分解によるポリマー劣化が発生したためと考えられる。また、これのＵ％も１６％と極度に悪いものであった。
【０１２９】
この共重合ＰＥＴアロイ繊維を経糸及び緯糸に用いて平織りを作成したが、糸切れや毛羽が頻発し、工程通過性が極端に悪く、また品位の悪い織物しか得られなかった。そして、この織物を９０℃の６重量％ＮａＯＨ水溶液で２時間処理し海綿状の繊維を得た。しかし、これは強度が０．３ｃＮ／ｄｔｅｘと極端に低強度であった。これは、元々、共重合ＰＥＴが熱劣化しているのに加え、高濃度のアルカリで長時間処理したために共重合ＰＥＴがボロボロに崩れてしまったためと考えられる。
【０１３０】
このように、ポリマーに適した混練、紡糸条件を設定しないと高強度で糸斑の小さな糸が得られず、製糸性も悪化してしまう。また、易溶解性ポリマーと難溶解性ポリマーの溶解度差が小さいとやはり低強度化の要因となる。以上のように、混練、紡糸、溶解条件をポリマー毎に最適化して初めて実用に耐えうる繊維が得られるのである。
【０１３１】
【表１】

【０１３２】
【表２】

【０１３３】
実施例１５
融点２５５℃、極限粘度０．６３、溶融粘度８３０ｐｏｉｓｅ（２８０℃、２４３２ｓｅｃ^−１）のホモＰＥＴを８０重量％、実施例９で用いた熱水可溶性ポリマーを２０重量％として２７５℃で実施例１と同様に二軸押出混練機を用いて溶融混練を行った。これを溶融部２の温度を２８０℃、紡糸温度を２８０℃とし、単孔吐出量と口金孔数を変更して実施例３と同様に溶融紡糸を行ったところ、紡糸性は良好で２４時間の連続紡糸の間の糸切れはゼロであった。そして、第１ホットローラー温度１６を９０℃として、実施例３と同様に延伸・熱処理を行い、９０ｄｔｅｘ、３６フラメント、強度３．３ｃＮ／ｄｔｅｘ、伸度４０％、Ｕ％１．５％、熱収縮率７％のポリマーアロイ繊維を得た。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察した結果（図２１）、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。ここで、濃い部分がＰＥＴ、薄い部分が熱水可溶性ポリマーである。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。また、糸物性は表４に示すとおり優れたものであった。
【０１３４】
このポリマーアロイ繊維を実施例９と同様に丸編み後、１００℃の熱水で２時間処理し熱水可溶性ポリマーの９９％以上を除去し、ＰＥＴナノポーラスファイバーからなる丸編みを得た。
【０１３５】
このＰＥＴナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果（図２２）、細孔の平均直径は２０ｎｍであり、直径が５０ｎｍ以上の大きな細孔は皆無であった。ここで、濃い部分がＰＥＴ、薄い部分が細孔であり、細孔は独立孔であった。ナノポーラスファイバーの物性は表３に示した。
【０１３６】
また、このＰＥＴナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。
【０１３７】
実施例１６
ホモＰＥＴをＰＥＧ１０００を８重量％、イソフタル酸を７ｍｏｌ％共重合したＰＥＴ（融点２３５℃、極限粘度０．６５溶融粘度９２０ｐｏｉｓｅ（２８０℃、２４３２ｓｅｃ^−１））として２５５℃で実施例１５と同様に溶融混練を行った。これを溶融部２の温度を２５５℃、紡糸温度を２５５℃、口金孔形状をＹ断面として実施例１５と同様に溶融紡糸を行ったところ、紡糸性は良好で２４時間の連続紡糸の間の糸切れはゼロであった。そして、実施例１５と同様に延伸・熱処理を行い三葉断面のポリマーアロイ繊維を得た。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。また、糸物性は表４に示すとおり優れたものであった。
【０１３８】
このポリマーアロイ繊維を実施例１５と同様に丸編み後、１００℃の熱水で２時間処理し熱水可溶性ポリマーの９９％以上を除去し、ＰＥＴナノポーラスファイバーからなる丸編みを得た。
【０１３９】
このＰＥＴナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果、細孔の平均直径は２０ｎｍであり、直径が５０ｎｍ以上の大きな細孔は皆無であった。ＴＥＭ観察から、細孔は独立孔であることがわかった。ナノポーラスファイバーの物性は表３に示した。
【０１４０】
また、このＰＥＴナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。
【０１４１】
実施例１７、１８
共重合ＰＥＴを融点２２０℃、溶融粘度１２９０ｐｏｉｓｅ（２８０℃、２４３２ｓｅｃ^−１）のポリトリメチレンテレフタレート（ＰＴＴ）または融点２２０℃、溶融粘度５５０ｐｏｉｓｅ（２８０℃、２４３２ｓｅｃ^−１）のポリブチレンテレフタレート（ＰＢＴ）として、実施例１５と同様に、溶融混練、溶融紡糸、延伸・熱処理を行った。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。また、糸物性は表４に示すとおり優れたものであった。
【０１４２】
このポリマーアロイ繊維を実施例１５と同様に丸編み後、１００℃の熱水で２時間処理し熱水可溶性ポリマーの９９％以上を除去し、ポリエステルナノポーラスファイバーからなる丸編みを得た。
【０１４３】
このポリエステルナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果、細孔の平均直径は２０ｎｍであり、直径が５０ｎｍ以上の大きな細孔は皆無であった。ＴＥＭ観察から、細孔は独立孔であることがわかった。ナノポーラスファイバーの物性は表３に示した。
【０１４４】
また、このポリエステルナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。
【０１４５】
実施例１９
ＰＥＴを融点１７０℃、溶融粘度１２００ｐｏｉｓｅ（２８０℃、２４３２ｓｅｃ^−１）の重量平均分子量１６万のＰＬＡとし、溶融温度を２２０℃として実施例１５と同様に溶融混練を行った。これを溶融部２の温度を２２０℃、紡糸温度を２２０℃として実施例１５と同様に溶融紡糸を行ったところ、紡糸性は良好で２４時間の連続紡糸の間の糸切れはゼロであった。そして、第１ホットローラー温度１６を９０℃として、実施例３と同様に延伸・熱処理を行った。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。また、糸物性は表４に示すとおり優れたものであった。
【０１４６】
このポリマーアロイ繊維を実施例１５と同様に丸編み後、１００℃の熱水で２時間処理し熱水可溶性ポリマーの９９％以上を除去し、ＰＬＡナノポーラスファイバーからなる丸編みを得た。
【０１４７】
このＰＬＡナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果、細孔の平均直径は２０ｎｍであり、直径が５０ｎｍ以上の大きな細孔は皆無であった。ナノポーラスファイバーの物性は表３に示した。
【０１４８】
また、このＰＬＡナノポーラスファイバーからなる丸編みに染色を施し発色性評価を行ったが、発色性に優れたものであった。特にＰＬＡは染料吸尽率が低いという問題があったが、ナノポーラス化することにより染料吸尽率が向上し、通常のＰＬＡ繊維より発色性が向上した。
【０１４９】
実施例２０、２１
ＰＬＡをポリプロピレン（ＰＰ）またはポリメチルメタクリレート（ＰＭＭＡ）として実施例１７と同様に溶融混練、溶融紡糸、延伸・熱処理を行った。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。また、糸物性は表４に示すとおり優れたものであった。
【０１５０】
このポリマーアロイ繊維を実施例１５と同様に丸編み後、１００℃の熱水で２時間処理し熱水可溶性ポリマーの９９％以上を除去し、ＰＰまたはＰＭＭＡナノポーラスファイバーからなる丸編みを得た。ナノポーラスファイバーの物性は表３に示した。
【０１５１】
実施例２２
ＰＥＴをポリメチルペンテン（ＰＭＰ）とし、溶融温度を２５５℃として実施例１５と同様に溶融混練を行った。これを溶融部２の温度を２５５℃、紡糸温度を２５５℃として実施例１５と同様に溶融紡糸を行ったところ、紡糸性は良好で２４時間の連続紡糸の間の糸切れはゼロであった。そして、第１ホットローラー温度１６を９０℃として、実施例３と同様に延伸・熱処理を行った。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比は１．２％であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。また、糸物性は表４に示すとおり優れたものであった。
【０１５２】
このポリマーアロイ繊維を実施例１５と同様に丸編み後、１００℃の熱水で２時間処理し熱水可溶性ポリマーの９９％以上を除去し、ＰＭＰナノポーラスファイバーからなる丸編みを得た。
【０１５３】
このＰＭＰナノポーラスファイバーの繊維横断面をＴＥＭで観察した結果、細孔の平均直径は３０ｎｍであり、直径が５０ｎｍ以上の大きな細孔の面積は細孔全体に対し０．３％であった。ナノポーラスファイバーの物性は表３に示した。
【０１５４】
実施例２３
ＰＥＴをポリフェニレンサルファイド（ＰＰＳ）、熱水可溶性ポリマーを実施例２で用いたＮ６とし、ＰＰＳのブレンド比を９０重量％として実施例１５と同様に３０５℃で溶融混練を行った。これを溶融部２の温度を３０５℃、紡糸温度を３０５℃とし、単孔あたりの吐出量と口金孔数を変更して実施例１５と同様に溶融紡糸を行ったところ、２４時間の連続紡糸の間の糸切れは２回であった。そして、第１ホットローラー温度１６を９０℃として、実施例３と同様に延伸・熱処理を行い、１５０ｄｔｅｘ、４８フィラメントのポリマーアロイ繊維を得た。得られたポリマーアロイ繊維の繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は１．５％であった。また、繊維縦断面ＴＥＭ観察から島は筋状構造をしていることがわかった。また、糸物性は表４に示すとおり優れたものであった。
【０１５５】
このポリマーアロイ繊維を実施例１５と同様に丸編み後、ギ酸で２時間処理しＮ６の９９％以上を除去し、ＰＰＳナノポーラスファイバーからなる丸編みを得た。ナノポーラスファイバーの物性は表３に示した。
【０１５６】
【表３】

【０１５７】
【表４】

【０１５８】
実施例２４
実施例１で作製したＮ６／共重合ＰＥＴアロイ仮撚り加工糸を鞘糸として用いて、オペロンテックス社製ポリウレタン繊維糸である“ライクラ”（登録商標）をカバリングした。そして、このカバリング糸を用いてタイツ用の編み地を作製した後、実施例１と同様にアルカリ処理を行いＮ６ナノポーラスファイバーからなるタイツ用編み地を作製した。このタイツ用編み地の目付は１００ｇ／ｍ^２であり、Ｎ６ナノファイバーとポリウレタン繊維糸の重量比率はそれぞれ９５％と５％であった。これにシリコーン処理、揉布処理を行った。そして、このタイツ用編み地を縫製し、タイツを作製した。このタイツからＮ６ナノポーラスファイバーを抜き出し、ＴＥＭ観察したところ、直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は２５ｎｍであった。また、細孔は独立孔であった。また、糸強度は２．５ｃＮ／ｄｔｅｘであった。このタイツは発色性も良好であり、ΔＭＲが５．６％と高く、また繊細なタッチと人肌のようなしっとりとしたみずみずしい風合いを示し、非常に着用快適性の高いものであった。また、ポリウレタン繊維を混用することにより、大きなストレッチ性が付与されただけでなく、洗濯時のタイツの形態安定性も向上した。
【０１５９】
実施例２５
単孔吐出量、孔数を変更し、紡糸速度を３８００ｍ／分として実施例１と同様に溶融紡糸を行い、４００ｄｔｅｘ、９６フィラメントのＮ６／共重合ＰＥＴポリマーアロイ繊維からなる高配向未延伸糸を得た。このポリマーアロイ高配向未延伸糸の強度は２．５ｃＮ／ｄｔｅｘ、伸度は１００％、Ｕ％は１．２％であった。この繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、また島の平均直径は３９ｎｍであった。そして、これに図２７の装置を用いて実施例１と同様に延伸仮撚りを施し、３３３ｄｔｅｘ、９６フィラメントの仮撚り加工糸を得た。得られた仮撚り加工糸は、強度３．０ｃＮ／ｄｔｅｘ、伸度３０％であった。得られたポリマーアロイ捲縮糸の繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。また、島の平均直径は２７ｎｍであった。
【０１６０】
この仮撚り加工糸に３００ターン／ｍの甘撚りを施し、Ｓ撚り／Ｚ撚り双糸で経糸および緯糸に用いて、２／２のツイル織物を作製した。そして、得られたツイル織物に実施例１と同様にアルカリ処理を施し、Ｎ６ナノポーラスファイバーからなる目付１５０ｇ／ｍ^２のカーテン用生地を得た。このカーテン用生地からＮ６ナノポーラスファイバーを抜き出し、ＴＥＭ観察したところ、直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は２５ｎｍであった。また、細孔は独立孔であった。また、糸強度は２．５ｃＮ／ｄｔｅｘであった。
【０１６１】
また、このカーテンは発色性も良好であり、吸湿率（ΔＭＲ）は５．５％と十分な吸湿性を示した。そして、この生地を用いてカーテンを作製し６畳間に吊したところ、高吸湿性により結露を抑制し、さらに悪臭ガスを消臭することにより、爽やかな室内環境とすることができた。このように、本発明のナノポーラスファイバーは、従来にない室内環境を整えることができる環境応答型のインテリア製品に好適であった。また、このカーテンを家庭用洗濯機で洗濯ネットに入れて洗濯・脱水したが形くずれは発生せず、レーヨン製のカーテンとは異なり、高吸湿性、高吸水性ではあっても良好な寸法安定性を示した。
【０１６２】
実施例２６
単孔吐出量、孔数を変更し、吐出孔をＹ型として実施例３と同様に溶融紡糸を行った。紡出糸は９００ｍ／分で引き取り、次いで、１段目の延伸倍率を１．３倍、トータル倍率を３．５倍の条件で２段延伸を行い、さらにジェットノズルを用いて捲縮を付与してから５００ｄｔｅｘ、９０フィラメントの嵩高加工糸を巻き取った。この嵩高加工糸の強度は５．０ｃＮ／ｄｔｅｘ、伸度は２５％であった。得られたポリマーアロイ捲縮糸の繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の面積比も０．１％以下であった。また、島の平均直径は３０ｎｍであった。
【０１６３】
得られた嵩高加工糸を２本引き揃えて合糸し、下撚り（２００Ｔ／ｍ）し、それを２本用いて上撚り（２００Ｔ／ｍ）で撚り合わせ、乾熱１７０℃で撚り止め処理を施した後、カットパイルカーペットとして公知の方法にてタフトした。このときには、通常のレベルカットにて、１／１０ゲージ、目付が１５００ｇ／ｍ^２となるようにステッチを調節してタフトした。その後、バッキングを実施した。タフトに際し、基布にはアクリル繊維とポリエステル繊維の混紡糸を用いた織り基布を使用した。さらにカットパイル部分のみをアルカリ処理し、カットパイル部分がＮ６ナノポーラスファイバーとなる構造を発現させた。これをＴＥＭ観察したところ、直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は３０ｎｍであった。また、細孔は独立孔であった。また、カットパイルを抜き出し強度を測定したところ、２．０ｃＮ／ｄｔｅｘであった。このカットパイル部分は発色性も良好であり、ΔＭＲは５．３％と十分な吸湿性を示し、爽やかな室内環境とすることができ、さらに結露も抑制できるものであった。
【０１６４】
実施例２７
口金および単孔吐出量を変更して実施例３と同様に紡糸を行い、第１引き取りローラー８にて糸を引き取った後、合糸し、バンカーに受けた。そして、バンカーに受けた糸条をさらに合糸し１５万ｄｔｅｘのトウとした。これを、９０℃水槽中で３．２倍に延伸した。そして、クリンパーを通した後、給油し、カットした。得られたカットファイバーは、単糸繊度７ｄｔｅｘ、捲縮数１０個／２５ｍｍ、繊維長５１ｍｍであった。捲縮数はカットファイバー単糸３０ｍｍをサンプリングし、捲縮数を数えた。このカットファイバーの強度は３．３ｃＮ／ｄｔｅｘ、伸度は４０％であった。これの繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍ以上の島の面積比は０．７％であった。また島の平均直径は３３ｎｍであった。
【０１６５】
このカットファイバーをカードで解繊した後クロスラップウェーバーでウェッブとした。次にニードルパンチ（１５００回／ｃｍ^２）を行い、１８０ｇ／ｍ^２の繊維絡合不織布とした。この不織布に実施例３と同様にアルカリ処理を施し、Ｎ６ナノポーラスファイバー不織布を得た。この不織布からナノポーラスファイバーをサンプリングしＴＥＭ観察したところ、直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は３０ｎｍであった。また、細孔は独立孔であった。また、カットファイバーをアルカリ処理し、ナノファイバー化したものの強度を測定したところ、２ｃＮ／ｄｔｅｘであった。この不織布は発色性も良好であり、ΔＭＲ＝５．８％と充分な吸湿性を示した。
【０１６６】
実施例２８
実施例２７で作製したポリマーアロイからなるカットファイバーを紡績し、ポリマーアロイ紡績糸を得た。これを経糸および緯糸に用いて目付１５０ｇ／ｍ^２の平織りを得た。そして、実施例１と同様にアルカリ処理を行いＮ６ナノポーラスファイバー布帛を得た。この布帛からナノポーラスファイバーをサンプリングしＴＥＭ観察したところ、直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は３０ｎｍであった。また、細孔は独立孔であった。また、この布帛からナノポーラスファイバー紡績糸を抜き出し強度を特定したところ、２．０ｃＮ／ｄｔｅｘであった。この布帛は発色性も良好であり、ΔＭＲ＝５．８％と充分な吸湿性を示し、また発色性も良好であった。
【０１６７】
実施例２９
実施例２０と同様に紡糸を行い、エアーサッカーにより糸条を引き取り、開繊させてネットに捕集した後、カレンダーロールを掛けポリマーアロイ繊維からなる目付３５ｇ／ｍ^２の不織布を得た。なお、エアーサッカーで引き取った繊維の単糸繊度は２ｄｔｅｘであり、繊度から求めた紡糸速度は４５００ｍ／分相当であった。この不織布からポリマーアロイ繊維を抜き取り繊維横断面をＴＥＭで観察した結果、粗大な凝集ポリマー粒子を含まず、直径が２００ｎｍ以上の島の島全体に対する面積比は０．１％以下、直径１００ｎｍの島の面積比も０．１％以下であった。また島の平均直径は３１ｎｍであった。
【０１６８】
この不織布に実施例１４と同様に熱水処理を施し、ＰＰナノポーラスファイバー不織布を得た。これは、吸水性に優れるものであった。この不織布からナノポーラスファイバーをサンプリングしＴＥＭ観察したところ、直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は３０ｎｍであった。このように、本発明のナノポーラスファイバーは、従来にない高機能不織布を得るために最適であった。
【０１６９】
実施例３０
実施例１４で作製したポリマーアロイ繊維と７０ｄｔｅｘ、９６フィラメントの通常のＮ６繊維をインターレースノズルを用いてエア混繊した。これを経糸および緯糸に用いて目付１５０ｇ／ｍ^２の平織りを作製し、実施例３と同様にアルカリ処理を施すことによりＮ６ナノポーラスファイバーと通常Ｎ６からなる布帛を得た。このＮ６ナノポーラスファイバーをＴＥＭ観察したところ、直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は２０ｎｍ、糸強度は３．３ｃＮ／ｄｔｅｘであった。また、細孔は独立孔であった。この布帛は発色性も良好であり、またΔＭＲも４％と充分な吸湿性を示した。また、これはソフトで繊細なタッチの優れた風合いであった。
【０１７０】
実施例３１
吐出量と口金孔数を変更し実施例３と同様に溶融紡糸を行い、９０ｄｔｅｘ、６８フィラメント、強度２．７ｃＮ／ｄｔｅｘ、伸度１００％、Ｕ％１．３％のポリマーアロイからなる高配向未延伸糸を巻き取った。これと別途準備した７０ｄｔｅｘ、３４フィラメントの通常のＮ６延伸糸（強度６ｃＮ／ｄｔｅｘ、伸度４５％）を複合仮撚りした。この時、延伸倍率は１．０２倍、ヒーター温度は１６５℃とした。得られたＣＲ３７％の複合仮撚り糸を用いて実施例１と同様に丸編みを作製し、アルカリ処理を施した。得られた丸編みからＮ６ナノポーラスファイバーを抜き出しＴＥＭ観察したところ、直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は１５ｎｍ、糸強度は２．５ｃＮ／ｄｔｅｘであった。また、細孔は独立孔であった。この布帛は発色性も良好であり、またΔＭＲも４．５％と充分な吸湿性を示した。また、これはソフトで繊細なタッチの優れた風合いであった。
【０１７１】
実施例３２
実施例４で得たポリマーアロイ繊維を経糸に７２ｄｔｅｘ、２７フィラメントのビスコースレーヨン緯糸に用い、目付が１５０ｇ／ｍ^２となるように２／２ツイル織物を作製した。これを実施例１と同様にアルカリ処理をほどこした。得られた布帛からＮ６ナノポーラスファイバーを抜き出しＴＥＭ観察したところ、直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は１５ｎｍ、糸強度は２．５ｃＮ／ｄｔｅｘであった。また、細孔は独立孔であった。この布帛は発色性も良好であり、またΔＭＲも７％と充分な吸湿性を示した。また、これはソフトで繊細なタッチの優れた風合いであった。このように、本発明のナノポーラスファイバーは他の繊維と混用することにより、さらに風合いや吸湿性を向上させることができ、高級衣料用の布帛に最適である。
【０１７２】
実施例３３
実施例１５で得たＰＥＴナノポーラスファイバーからなる布帛に吸湿剤である高松油脂（株）製商品名“ＳＲ１０００”（１０％水分散品）を吸尽させた。このときの、加工条件は吸湿剤は固形分として２０％ｏｗｆ、浴比１：２０、処理温度１３０℃、処理時間１時間とした。この吸湿剤の通常のポリエステル繊維への吸尽率はほぼ０％であるが、このＰＥＴナノポーラスファイバーへの吸尽率は１２％以上であり、ΔＭＲ＝４％以上と綿同等以上の優れた吸湿性を有するＰＥＴ布帛を得ることができた。このように、本発明のナノポーラスファイバーは、機能物質を容易に取り込み、あたかもカプセル化するような構造となるため、機能物質の吸尽率を向上することができ、機能加工用原糸として最適である。
【０１７３】
比較例６
通常のＰＥＴ布帛を実施例３３と同様に吸湿加工を施したが、吸湿剤の吸尽率はほぼ０％であり、吸湿性も発現しなかった。
【０１７４】
実施例３４
実施例１５で作製したＰＥＴナノポーラスファイバーからなる布帛に難燃剤であるトリフェニルリン酸（味の素ファインテクノ（株）“レオフォスＴＰＰ”）を２０％ｏｗｆ、浴比１：４０、処理温度１３０℃、処理時間１時間で吸尽させた。そして、これを水洗後、炭酸ナトリウム水溶液（８０℃）でソーピングした。さらに、家庭洗濯を１０回施した。このときの付着量は７重量％であり、燃焼評価を行ったところ良好な自己消火性を示したこのように、本発明のナノポーラスファイバーは、機能物質を容易に取り込み、あたかもカプセル化するような構造となるため、洗濯耐久性を向上することができ、機能加工用原糸として最適である。
【０１７５】
比較例７
通常のＰＥＴ布帛を実施例３４と同様に難燃加工を施した。これの洗濯１０回後の付着量は１重量％であり、燃焼評価を行ったところ自己消火性を示さなかった。
【０１７６】
実施例３５
実施例１５で得たＰＥＴナノポーラスファイバーからなる布帛に鮫の肝臓から抽出した天然油成分であり、保湿によるスキンケア効果のあるスクワランを吸尽させた。この時の処理条件は、スクワラン６０％と乳化分散剤４０％を混合した物を水に濃度７．５ｇ／リットルで分散させ、浴比１：４０、温度１３０℃、処理時間６０分間である。処理後８０℃で２時間洗浄を行い、この時のスクワランの付着量は布帛に対して２１重量％であった。その後、家庭洗濯を２０回施した後のスクワランの付着量は、布帛に対して１２重量％であり、充分な洗濯耐久性を示した。
【０１７７】
このスクワラン加工されたＰＥＴナノポーラスファイバーからなる丸編みを用いて靴下を作製し、かかとの乾燥がひどい被験者１０人に１週間の着用試験を行ったところ、乾燥肌が緩和された者が８人いた。これは、細孔にトラップあるいはカプセル化されたスクワランが被験者の汗により徐々に抽出され、肌と接触したためと考えられる。
【０１７８】
比較例８
通常のＰＥＴ布帛に実施例３６と同様にスクワランの吸尽加工を施したところ、洗浄後の付着量は布帛に対して２１重量％であったが、家庭洗濯１０回後の付着量は０重量％であり、まったく洗濯耐久性が無かった。
【０１７９】
実施例３６
実施例３で作製したＮ６ナノポーラスファイバー布帛をイオン交換水に浸漬し、その後１，２−ビス（トリメトキシシリル）エタンを加え、３時間攪拌した。室温で１４時間静置後、さらに１３時間攪拌し、さらに室温で１４時間静置後、さらに７時間攪拌し、シリカを重合した。その後、丸編み地をイオン交換水で洗浄後、風乾した。この操作により、Ｎ６ナノファイバーの細孔を鋳型とした、布帛形状のＮ６／シリカ複合体が得られた。これは、十分な剛性としなやかさを併せ持つ優れた材料であった。また、優れた難燃性を持つハイブリッド材料でもあった。また、この複合体中のシリカの比率は３０重量％であった。
【０１８０】
このように、本発明のナノポーラスファイバーは、重合性あるいは架橋性のあるモノマーやオリゴマーを吸尽した後、これらを重合あるいは架橋することで容易にハイブリッド材料とすることができる。このため、無機材料の機能（難燃、触媒等）を有する有機材料や柔軟性を有する無機材料等の先端材料を得るための前駆体に最適である。
【０１８１】
実施例３７
実施例２４で作製したＮ６ナノポーラスファイバーからなるタイツに大鵬薬品社製「新ポリカイン液」を含浸させ、乾燥した。これにより、水虫薬を汗により溶出させることができるタイツを得た。このタイツを水虫患者に着用させ、一日ごとに新品に取り替えた。これを１ヶ月続けたところ、水虫薬が徐放されたため症状の改善が見られた。
【０１８２】
このように、本発明のナノポーラスファイバーは、薬効成分の徐放能力があるため、メディカル製品として好適である。
【０１８３】
実施例３８
実施例１で得たＮ６ナノポーラスファイバー布帛の消臭試験を以下の手法で行った。すなわちサンプル布帛３．０ｇを５００ｍｌのポリエチレン製容器内に固定した後、悪臭物質を容器内に導入した。そして、密栓後、容器を５０℃で１分間保持し、悪臭物質を十分気化させた。そして、３０℃で所定時間放置後、容器内の空気をサンプリングし、株式会社ガステック社製のガス検知管で悪臭物質濃度を測定した。悪臭物質としてアンモニアを使用した場合、初期濃度２００ｐｐｍから１０分間で２０ｐｐｍまで消臭できた。また、硫化水素ガスを用いた場合には初期濃度４５ｐｐｍから１０分間で２ｐｐｍまで消臭できた。
【０１８４】
比較例９
通常のＮ６布帛を用いて実施例３９と同様に消臭試験を行ったところ、アンモニアでは初期濃度２００ｐｐｍから１０分間で１３０ｐｐｍ、また、硫化水素ガスを用いた場合には初期濃度４５ｐｐｍから１０分間で１０ｐｐｍまでしか消臭できなかった。
【０１８５】
実施例３９
実施例１で得たＮ６ナノポーラスファイバー布帛をジエチレントリアミン３％水溶液に５０℃で１分間浸漬することにより、Ｎ６ナノポーラスファイバーにジエチレントリアミンを担持させた。これのアセトアルデヒド除去能力を評価したところ、１０分間で３０ｐｐｍから１ｐｐｍまで濃度が低下し、優れた除去能力を示した。
【０１８６】
このように、本発明のナノポーラスファイバーは、吸着剤の坦持能力があるため、ケミカルフィルターやエアフィルター等の産業資材製品として好適である。
【０１８７】
実施例４０
実施例１で作製したポリマーアロイを芯成分、実施例１で用いたＮ６を鞘成分としてそれぞれ２７０℃で溶融した後、紡糸温度２７５℃で芯鞘複合紡糸を行い、３８００ｍ／分で引き取り高配向未延伸糸を得た。これに実施例１と同様に延伸仮撚りを施した。ここでポリマーアロイの複合比は８０重量％とした。得られた芯鞘複合捲縮糸は１５０ｄｔｅｘ、７６フィラメント、強度４．０ｃＮ／ｄｔｅｘ、伸度２７％、Ｕ％１．０％、熱収縮率１０％、ＣＲ４５％であった。芯成分であるポリマーアロイ中で島共重合ＰＥＴは平均直径２６ｎｍ程度で微分散し、直径１００ｎｍ以上の粗大な島は島全体に対し面積比で０．１％以下であった。ここで得られた芯鞘複合捲縮糸を用い実施例１と同様に丸編み、アルカリ処理を行い、Ｎ６ナノポーラスファイバーからなる丸編みを得た。これからナノポーラスファイバーを抜き取り、ＴＥＭ観察したところ直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は２０ｎｍであった。また、ナノポーラス部の面積は繊維横断面に対して７７％であった。また、ナノポーラスファイバーの糸強度は３．３ｃＮ／ｄｔｅｘであり、実施例１に比べ高強度であり、耐摩耗性にも優れていた。また、細孔は独立孔であった。この布帛は実施例１よりも鮮明発色となり、またΔＭＲも４．８％と充分な吸湿性を示した。
【０１８８】
実施例４１
芯成分と鞘成分を入れ替え、ポリマーアロイの複合比を５０重量％として実施例４１と同様に芯鞘複合紡糸、延伸仮撚りを行い、１５０ｄｔｅｘ、７６フィラメント、強度４．１ｃＮ／ｄｔｅｘ、伸度２７％、Ｕ％１．０％、熱収縮率１０％、ＣＲ４５％の芯鞘複合捲縮糸を得た。鞘成分であるポリマーアロイ中で島共重合ＰＥＴは平均直径２６ｎｍ程度で微分散し、直径１００ｎｍ以上の粗大な島は島全体に対し面積比で０．１％以下であった。ここで得られた芯鞘複合捲縮糸を用い実施例４１と同様に丸編み、アルカリ処理を行い、Ｎ６ナノポーラスファイバーからなる丸編みを得た。これからナノポーラスファイバーを抜き取り、ＴＥＭ観察したところ直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は２０ｎｍであった。また、ナノポーラス部の面積は繊維横断面に対して４５％であった。また、ナノポーラスファイバーの糸強度は３．５ｃＮ／ｄｔｅｘであり、実施例１に比べ高強度であった。また、細孔は独立孔であった。この布帛は発色性も良好であり、またΔＭＲも４％と充分な吸湿性を示した。
【０１８９】
実施例４２
Ｎ６単独側を実施例５で用いた高粘度Ｎ６とし、ポリマーアロイを実施例１で作製したものとして、５０重量％／５０重量％の複合比でサイドバイサイド複合として実施例４１と同様に複合紡糸を行った。得られ未延伸糸を延伸倍率１．２倍で実施例３と同様に延伸・熱処理し、１１０ｄｔｅｘ、３４フィラメント、強度４．１ｃＮ／ｄｔｅｘ、伸度２７％、Ｕ％１．２％、熱収縮率１０％、捲縮数２０個／２５ｍｍのサイドバイサイド捲縮糸を得た。捲縮の外側の成分であるポリマーアロイ中で島共重合ＰＥＴは平均直径２６ｎｍ程度で微分散し、直径１００ｎｍ以上の粗大な島は島全体に対し面積比で０．１％以下であった。ここで得られたサイドバイサイド捲縮糸を用い実施例と同様に丸編み、アルカリ処理を行い、Ｎ６ナノポーラスファイバーからなる丸編みを得た。これからナノポーラスファイバーを抜き取り、ＴＥＭ観察したところ直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は２０ｎｍであった。また、ナノポーラス部の面積は繊維横断面に対して４４％であった。また、ナノポーラスファイバーは充分な嵩高性を有し、糸強度３．５ｃＮ／ｄｔｅｘと高強度であった。また、細孔は独立孔であった。この布帛は発色性も良好であり、またΔＭＲも４％と充分な吸湿性を示した。また、この布帛は吸水するとさらに嵩高性が向上した。
【０１９０】
実施例４３
Ｎ６単独側を実施例１で用いた低粘度Ｎ６とし、ポリマーアロイ側を実施例５で作製したものとして実施例４３と同様に複合紡糸、延伸・熱処理を行い、１１０ｄｔｅｘ、３４フィラメント、強度４．０ｃＮ／ｄｔｅｘ、伸度２５％、Ｕ％１．２％、熱収縮率１０％、捲縮数１８個／２５ｍｍのサイドバイサイド捲縮糸を得た。捲縮の内側の成分であるポリマーアロイ中で島共重合ＰＥＴは平均直径１８ｎｍで微分散し、直径１００ｎｍ以上の粗大な島は島全体に対し面積比で０．１％以下であった。ここで得られたサイドバイサイド捲縮糸を用い、実施例４１と同様に丸編み、アルカリ処理を行い、Ｎ６ナノポーラスファイバーからなる丸編みを得た。これからナノポーラスファイバーを抜き取り、ＴＥＭ観察したところ直径が５０ｎｍ以上の粗大細孔は皆無であり、細孔の平均直径は２０ｎｍであった。また、ナノポーラス部の面積は繊維横断面に対し４５％であった。また、ナノポーラスファイバーは充分な嵩高性を有し、糸強度も３．４ｃＮ／ｄｔｅｘと高強度であった。また、細孔は独立孔であった。この布帛は、発色性も良好であり、またΔＭＲも４％と充分な吸湿性を示した。また、この布帛は吸水すると、捲縮が伸び編目が拡がり、通気性が向上した。
【０１９１】
実施例４４
実施例３で得たポリマーアロイ繊維からなる丸編みを、２％の水酸化ナトリウム水溶液（９５℃、浴比１：４０）で２０分間処理し、ポリマーアロイ繊維中の共重合ＰＥＴの５０％を分解溶出した（繊維としての重量減量率は１０％）。溶出は繊維表層からリング状に進行し、ナノポーラス部は繊維横断面に対し５０％であった。この部分をＴＥＭ観察した結果、細孔は独立孔であり、これの平均直径は２０ｎｍであり、直径が５０ｎｍ以上の粗大細孔は皆無であった。
【０１９２】
この丸編みはΔＭＲ＝４．０％であった。着性を示した。また保水率も６０％と充分であった。これも可逆的水膨潤性を示したが、膨潤率は４％と低いものであり、実施例３に比べ寸法安定性が向上していた。
【０１９３】
実施例４５
実施例１で作製したポリマーアロイ捲縮糸を経糸および緯糸に用い、１７０ｇ／ｍ^２の高密度平織りを作製した。これに実施例１と同様にアルカリ処理を施し、Ｎ６ナノポーラスファイバーからなる平織りを作製した。これからナノポーラスファイバーを抜き取り、形態および物性を測定したところ、実施例１と同様の値が得られた。これに、バフィング処理を施したところナノポーラスファイバーの表層がフィブリル化し、繊維径０．０１〜１μｍ程度のフィブリルが多数生成し、織物表面を覆った。これにより、ソフトでスパン感のあるタッチが得られただけでなく、ノンコーティングでも撥水性が発現し、スポーツ用の布帛として好適であった。
【０１９４】
比較例１０
通常のＮ６仮撚り加工糸（７７ｄｔｅｘ、３４フィラメント）を用い、実施例４６と同様に高密度平織りを作製し、バフィングを施したがフィブリル化が不十分であり、フィブリルが織物表面を覆うことはなく、ピル（毛玉）が多くなり、表面外観が汚くなっただけでなく、ソフトでスパン感のあるタッチも得られなかった。また、フィブリル化を進めるためにバフィング処理をきつくすると布帛破れが生じてしまった。
【０１９５】
実施例４６
実施例１で作製したポリマーアロイ捲縮糸を緯糸に、経糸に通常Ｎ６繊維（４４ｄｔｅｘ、１２フィラメント）を用いて１８０ｇ／ｍ^２の５枚バックサテンを作製した。これに実施例１と同様にアルカリ処理を施し、Ｎ６ナノポーラスファイバーからなるバックサテン織物を作製した。これからナノポーラスファイバーを抜き取り、形態および物性を測定したところ、実施例１と同様の値が得られた。これに、バフィング処理を施した。これにより、ナノポーラスファイバーの表層がフィブリル化し、繊維径０．０１〜１μｍ程度のフィブリルが多数生成し、織物表面を覆った。この後、さらにウォーターパンチ処理を施し、フィブリルをさらに開繊させた。これは、ワイピングクロス等の生活資材製品用の布帛として好適であった。
【０１９６】
実施例４７
実施例２７で得たＮ６ナノポーラスファイバーからなる不織布にバフィング処理を施したところ、やはり繊維径０．０１〜１μｍ程度のフィブリルが多数生成し、不織布表面を覆った。これは従来のナイロン不織布にはないソフトな表面タッチであった。
【０１９７】
実施例４８
実施例２９で得たＰＰナノポーラスファイバーからなる不織布にバフィング処理を施したところ、繊維径０．０１〜１μｍ程度のフィブリルが多数生成し、不織布表面を覆った。これは従来のＰＰスパンボンド不織布よりも表面積が大きくなったため、粒子の補足効率やエレクトレット加工の効率が高くフィルターに好適な物であった。
【０１９８】
【発明の効果】
本発明の従粗大細孔をほとんど含まないナノ細孔が均一性に分散したナノポーラスファイバーにより、従来の多孔繊維に比べ発色性を大幅に向上でき、また優れた吸湿・吸着特性を活かした高付加価値の繊維製品を得ることができる。
【図面の簡単な説明】
【図１】実施例１のナノポーラスファイバー横断面を示すＴＥＭ写真である。
【図２】実施例１のポリマーアロイ繊維横断面を示すＴＥＭ写真である。
【図３】実施例３のポリマーアロイ繊維横断面を示すＴＥＭ写真である。
【図４】実施例３のポリマーアロイ繊維縦断面を示すＴＥＭ写真である。
【図５】実施例３のナノポーラスファイバー横断面を示すＴＥＭ写真である。
【図６】実施例３のナノポーラスファイバー縦断面を示すＴＥＭ写真である。
【図７】実施例３のポリマーアロイチップの断面を示すＴＥＭ写真である。
【図８】実施例６のポリマーアロイ繊維横断面を示すＴＥＭ写真である。
【図９】実施例６のナノポーラスファイバー横断面を示すＴＥＭ写真である。
【図１０】実施例７のポリマーアロイ繊維横断面を示すＴＥＭ写真である。
【図１１】実施例７のナノポーラスファイバー横断面を示すＴＥＭ写真である。
【図１２】実施例８のポリマーアロイ繊維横断面を示すＴＥＭ写真である。
【図１３】実施例８のナノポーラスファイバー横断面を示すＴＥＭ写真である。
【図１４】実施例１１のポリマーアロイ繊維の繊維横断面を示すＴＥＭ写真である。
【図１５】実施例１１のポリマーアロイ繊維横断面を示すＴＥＭ写真である。
【図１６】実施例１１のポリマーアロイ繊維縦断面を示すＴＥＭ写真である。
【図１７】実施例１１のナノポーラスファイバー横断面を示すＴＥＭ写真である。
【図１８】実施例１１のナノポーラスファイバー縦断面を示すＴＥＭ写真である。
【図１９】実施例１２のポリマーアロイ繊維横断面を示すＴＥＭ写真である。
【図２０】実施例１２のナノポーラスファイバー横断面を示すＴＥＭ写真である。
【図２１】実施例１５のポリマーアロイ繊維横断面を示すＴＥＭ写真である。
【図２２】実施例１５のナノポーラスファイバー横断面を示すＴＥＭ写真である。
【図２３】紡糸装置を示す図である。
【図２４】口金を示す図である。
【図２５】延伸装置を示す図である。
【図２６】紡糸装置を示す図である
【図２７】延伸仮撚り装置を示す図である。
【図２８】紡糸直接延伸装置を示す図である。
【符号の説明】
１：ホッパー
２：溶融部
３：紡糸パック
４：口金
５：チムニー
６：糸条
７：集束給油ガイド
８：第１引き取りローラー
９：第２引き取りローラー
１０：巻き取り糸
１１：計量部
１２：吐出孔長
１３：吐出孔径
１４：未延伸糸
１５：フィードローラー
１６：第１ホットローラー
１７：第２ホットローラー
１８：デリバリーローラー（室温）
１９：延伸糸
２０：静止混練器
２１：未延伸糸
２２：フィードローラー
２３：ヒーター
２４：冷却板
２５：回転子
２６：デリバリーローラー
２７：仮撚加工糸
２８：第１ホットローラー
２９：第２ホットローラー[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a nanoporous fiber having many fine and uniform nanopores, which hardly contains coarse pores that diffusely reflect visible light.
[0002]
[Prior art]
Polyamide fibers typified by nylon 6 (N6) and nylon 66 (N66) and polyester fibers typified by polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) have excellent mechanical properties and dimensional stability. Rather, it is widely used for interiors, vehicle interiors, industrial uses, and the like. In addition, polyolefin fibers represented by polyethylene (PE), polypropylene (PP) and the like are widely used for industrial applications by utilizing their lightness.
[0003]
However, there is a limit to the performance of a single polymer fiber. Therefore, polymer modification such as copolymerization or polymer blending, and compounding of functions by composite spinning or mixed fiber spinning have been studied. Among them, polymer blends have been studied particularly actively because there is no need to design a new polymer and the polymer blend can be produced using a single-component spinning machine.
[0004]
By the way, hollow fibers and porous fibers have been studied for the purpose of imparting lightness and water absorption to the fibers. The development of hollow fibers has been promoted with the aim of achieving a high hollow ratio, but there has been a problem that the hollows are crushed by false twisting or the like. For this reason, recently, a multi-island hollow fiber using a composite fiber with a water-soluble polymer has been developed. However, since the hollow diameter is 1 μm or more, scattering of visible light at the polymer / air interface in the hollow portion increases. In addition, there was a problem that the color developability of the fiber was significantly reduced.
[0005]
On the other hand, a porous fiber having a large number of sub-micrometer level pores has been studied, but a polymer blend spinning method instead of a composite spinning method has been adopted for this production method. For example, it is known that a nylon fiber having porosity can be obtained by blending nylon with a hydrophilic group copolymerized PET to form a fiber, and eluting the copolymerized PET therefrom (Patent Document 1). As a result, sub-micron level surface irregularities and pores are formed, so that pearl-like luster can be obtained, but on the contrary, there is a problem that the color developability is significantly reduced. This is because the pore size is at the level of the wavelength of visible light and the number of pores is large, so that the scattering of visible light is greater than that of the multi-island hollow fiber. There is also a fiber having pores having pore sizes smaller than visible light (Patent Document 2). However, in practice, coarse aggregated particles of PET are present in the blended fiber, and after the aggregated particles elute. Because of the existence of coarse pores of sub-μm to 1 μm level, there was also a problem of lowering of the coloring property as in Patent Document 1. In fact, the seventh line from the top and bottom left of page 2 of this document states that "polyester component is mostly present in the polyamide as streaks having a thickness of 0.01 to 0.1 [mu], and cavities of almost the same size exist after elution. And the presence of PET aggregated particles is pointed out. In addition, there are proposals of porous fibers using nylon / PET blend fibers (Patent Documents 3 and 4), but the dispersion size of PET in nylon is large, and the distribution of PET is about 0.1 to 1 μm. However, the problem of the decrease in color development due to the coarse pores could not be solved.
[0006]
In addition, when the pore size distribution is large as in the conventional example, the influence of the coarse pores in the entire pores increases rapidly, so that the contribution of the fine nanopores is small, and the effect of the pore formation is sufficient. There were also problems that could not be demonstrated.
[0007]
For this reason, a fiber having microporosity not containing coarse pores has been demanded.
[0008]
[Patent Document 1]
JP-A-2-175965 (pages 1 to 5)
[0009]
[Patent Document 2]
JP-A-56-107069 (pages 1 to 3)
[0010]
[Patent Document 3]
JP-A-8-158251 (pages 1 to 7)
[0011]
[Patent Document 4]
JP-A-8-296123 (pages 1 to 7)
[0012]
[Problems to be solved by the invention]
An object of the present invention is to provide a nanoporous fiber in which, unlike conventional porous fibers, nano-order fine pores containing almost no coarse pores are uniformly dispersed.
[0013]
[Means for Solving the Problems]
The above object is achieved by a nanoporous fiber having pores having a diameter of 100 nm or less, wherein the area ratio of pores having a diameter of 200 nm or more to the entire fiber cross section is 1.5% or less.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
Examples of the polymer constituting the nanoporous fiber of the present invention include polyesters, polyamides, thermoplastic polymers represented by polyolefins, thermosetting polymers such as phenolic resins, and polymers having poor thermoplasticity represented by polyvinyl alcohol and polyacrylonitrile. And a biopolymer, but a thermoplastic polymer is preferred from the viewpoint of moldability. Among them, polyesters and polyamides have many high melting points and are more preferable. It is preferable that the melting point of the polymer is 165 ° C. or higher, since the heat resistance is good. For example, polylactic acid (PLA) is 170 ° C., PET is 255 ° C., and N6 is 220 ° C. Further, the polymer may contain additives such as particles, a flame retardant, and an antistatic agent. Other components may be copolymerized as long as the properties of the polymer are not impaired. However, in order to maintain the inherent heat resistance and mechanical properties of the polymer, the copolymerization ratio must be 5 mol% or less by weight. Is preferred. In particular, when used for clothing, interiors, vehicle interiors, etc., polyesters and polyamides are preferred in terms of melting point, mechanical properties, and texture, and nylon 6 and nylon having a copolymerization ratio of 5 mol% or less and 5 wt% or less and a relative viscosity of 2 or more. 66, PET having an intrinsic viscosity of 0.50 or more, polytrimethylene terephthalate, polybutylene terephthalate, and PLA having a weight average molecular weight of 100,000 or more are particularly preferable. It is preferable that these polymers constitute 80% by weight or more of the nanoporous fiber.
[0015]
In the present invention, it is important that the nanoporous fiber has pores having a diameter of 100 nm or less. Here, the nanoporous fiber means that pores having a diameter of 100 nm or less are 1 / μm in the cross section of the fiber. ² The above is included. As a result, the water absorption can be dramatically increased.
[0016]
It is important that the area ratio of pores having a diameter of 200 nm or more in the entire fiber cross section is 1.5% or less. Since the wavelength of visible light is about 400 to 800 nm, the decrease in color developability of a nanoporous fiber can be significantly reduced by the absence of coarse pores having a diameter of 200 nm or more. Here, the diameter and area of the pores can be measured by cutting an ultrathin section of the nanoporous fiber and observing the section with a transmission electron microscope (TEM). Since the pores may be elliptical or other distorted shapes and are not necessarily a perfect circle, the diameter is determined by converting the pore area into a circle. Further, the entire fiber cross section is the area of the fiber cross section of the single fiber, and here is the area composed of the polymer portion and the pore portion. These areas can be easily obtained by using image processing software such as WINROOF. More preferably, the area ratio of pores having a diameter of 50 nm or more occupying the entire fiber cross section is 1.5% or less, further preferably 0.1% or less.
[0017]
The average diameter of the pores is preferably 0.1 to 50 nm. As a result, visible light hardly scatters and is transparent to visible light, but it approaches a harmful wavelength of ultraviolet light, so that a new function of UV cutting is developed. Furthermore, since the surface area of the fiber is dramatically increased, there is a great advantage that excellent moisture absorbency and adsorptivity, which could not be expected with the conventional porous fiber, are exhibited. In addition, when such a large number of micropores are present, the ability to absorb various liquids such as an organic solvent other than water is dramatically improved. From this viewpoint, the average diameter of the pores is more preferably 30 nm or less. However, if the pore diameter is too small, the pores are easily crushed by heat treatment or the like. Therefore, the average diameter of the pores is more preferably 5 nm or more.
[0018]
An example of the nanoporous fiber of the present invention is shown in FIG. 5 (a TEM photograph of a cross section of the N6 nanoporous fiber), and fine shading due to metal staining is observed. Here, the dark portion indicates the N6 high density region, and the light portion indicates the N6 low density region. Here, the light portion is considered to correspond to the pore. On the other hand, the longitudinal section of the N6 nanoporous fiber is shown in FIG. 6, and it can be seen that it shows a light and shade pattern in which grains are arranged like streaks. Further, these pores may be communication holes connected to each other or independent holes hardly connected. These pores can incorporate various molecules into the pores as described later, but considering the washing durability and sustained release properties of these pores, independent pores can trap or encapsulate the captured molecules to some extent. Is preferred.
[0019]
As described above, the nanoporous fiber has an innumerable number of nanopores, but has an advantage that the specific surface area is increased and excellent moisture absorption / adsorption is exhibited. The moisture absorption (ΔMR) of the nanoporous fiber is preferably 4% or more. In addition, the nanoporous fiber has excellent adsorption characteristics of various substances as well as water vapor, and is useful as a deodorant fiber. Furthermore, in addition to exhibiting the same level of water absorption as cotton, in some cases it exhibits reversible water swelling in the yarn longitudinal direction like wool. Is also possible. Here, the reversible water swelling property is a property of reversibly repeating water absorption swelling / drying shrinkage, in which the fiber expands in the longitudinal direction when water is absorbed, and shrinks to the original length when water is removed from the fiber by drying or the like. That's what it says. In the nanoporous fiber of the present invention, the swelling ratio in the yarn longitudinal direction at the time of water absorption swelling is preferably 6% or more. Fibers having such special properties are useful as comfortable clothing and the like. For example, in a case where a knitted fabric is produced using the same, when the fibers absorb the moisture of sweat and extend in the longitudinal direction of the yarn, the knit crimp is elongated, and as a result, the stitch is expanded. For this reason, the opening is enlarged in the knitted fabric, so that moisture and water vapor easily pass from the back of the knitted fabric to the front. As a result, the stuffiness of the clothes is greatly reduced, and the user feels comfortable. Further, such a knitted fabric has an excellent soil release property in which dirt due to washing is easily removed. This is because the fibers swell in the longitudinal direction and expand the stitches by absorbing water as described above, so that the dirt attached between the fibers can be easily removed.
[0020]
Further, since various functional substances are easily taken into the nanopores, the fibers are more easily processed than conventional fibers. For example, even if a polyethylene glycol (PEG) -based hygroscopic agent having a molecular weight of 1,000 or more is applied for the purpose of imparting hygroscopicity to a cloth made of ordinary polyester fibers, almost no exhaustion can occur. However, if the same moisture absorbent is applied to the cloth made of the PET nanoporous fiber of the present invention, a large amount of the cloth can be exhausted. Recently, squalane, a natural oil component obtained from shark liver, has been attracting attention as a substance having a skin care function by moisturizing. However, even if it is applied to a cloth made of ordinary polyester fiber, it can hardly be exhausted. Nevertheless, the fabric composed of the nanoporous fiber of the present invention can exhaust a large amount and greatly improve the washing durability. In addition, functional chemicals to be exhausted include not only hygroscopic agents and moisturizers, but also flame retardants, water repellents, cold insulators, warming agents, smoothing agents, fine particles, and polyphenols, amino acids, proteins, capsaicin, vitamins, and other health agents.・ Applicable to drugs for promoting beauty, drugs for skin diseases such as athlete's foot, disinfectants, drugs such as anti-inflammatory drugs and analgesics, and drugs for adsorbing and decomposing harmful substances such as polyamines and photocatalytic nanoparticles. it can. Further, it is also possible to exhaust a monomer having an organic or inorganic polymer forming ability and then polymerize the monomer to produce a hybrid material. In addition, it is of course possible to activate the pore wall surface by chemical processing by utilizing the wide specific surface area to have selective adsorption and catalytic ability.
[0021]
The strength of the nanoporous fiber of the present invention is preferably 1.5 cN / dtex or more, since the tear strength and durability of the fiber product can be improved. The strength is more preferably 2 cN / dtex or more, further preferably 2.5 cN / dtex or more. Further, it is preferable that the elongation is 20% or more because the durability of the fiber product can be improved.
[0022]
In addition, the nanoporous fiber of the present invention may be easily fibrillated by physical fuzzing such as buffing and water punching, and is also useful as a so-called fibrillated fiber or a fiber product comprising the same. At this time, the fibril diameter can be controlled in the range of 0.001 to 5 μm depending on the combination of the polymer in the polymer alloy fiber as the precursor, the physical properties of the polymer alloy fiber, the morphology of the pores in the nanoporous fiber, and the fluff processing conditions. It is. In particular, the morphology of the pores is important, and the smaller the pores are, the more likely they are to fibrillate. This is greatly affected by the blend size and blend ratio of the easily soluble polymer in the polymer alloy fiber as the precursor. In particular, fibers having good abrasion resistance, such as polyamide, have no fibrillated fibers and are useful.
[0023]
Further, the nanoporous fiber of the present invention can adopt various fiber cross-sectional shapes such as a trilobal cross section, a cross cross section, and a hollow cross section. Further, the nanoporous may be present on the entire surface of the fiber cross section, and the nanoporous portion may be unevenly present on the fiber surface layer side, the inner layer part, or the like. Here, the nanoporous portion is defined as one pore having a diameter of 100 nm or less / μm. ² This is an area including the above. When the fiber inner layer portion becomes a nanoporous portion and the fiber surface layer portion is a normal polymer, the abrasion resistance, dimensional stability, and strength can be improved. When the surface layer of the fiber is a nanoporous portion and the inner layer of the fiber is a normal polymer, dimensional stability and strength can be improved. Further, when the nanoporous portion occupies an eccentric and eccentric position, the fiber can be crimped. When the nanoporous portion occupies the outer portion of the crimp, the crimp is further strengthened by water absorption, and the stretchability and bulkiness are improved. On the other hand, when the nanoporous portion occupies the inner part of the crimp, the crimp is stretched by water absorption, so that the effect of stretching the yarn like wool is exhibited and the restraint of the fabric structure is loosened, or the stitch or weave is enlarged. Breathability is improved. Thus, when the nanoporous portion exists eccentrically in the fiber cross section, it is possible to provide a fabric that breathes by absorbing water. However, in the nanoporous fiber in which the nanoporous portion is localized, in order to achieve both the excellent performance of the nanopore and the characteristics of a normal polymer, the nanoporous portion has an area ratio of 5 to 95% with respect to the entire fiber cross section. Is preferred. The area ratio of the nanoporous portion is more preferably 20 to 80%, and further preferably 40 to 60%. Such a nanoporous fiber in which the nanoporous portion is localized, when eluting the easily soluble component from the polymer alloy fiber, stops the dissolution treatment halfway, leaving the easily soluble component in the fiber, or a composite spinning of the polymer alloy and the ordinary polymer. It can be obtained by eluting easily soluble components from the conjugated fiber.
[0024]
The nanoporous fiber of the present invention can be used alone, but can also be mixed with ordinary synthetic fiber, chemical fiber, natural fiber, or the like by blending, blending, blending, weaving, weaving and the like. When mixed with synthetic fibers having excellent dimensional stability and durability, it is possible to improve the form stability, durability and chemical resistance of the fabric. When mixed with a chemical fiber or a natural fiber, the moisture absorption / water absorption function and the texture can be further improved.
[0025]
In addition, the nanoporous fiber of the present invention may be a flat yarn without crimp or a crimped yarn, but when a crimped yarn is used, the obtained fabric can have bulkiness and stretchability, This is preferable because it can be used in a wide range of applications. Furthermore, various fiber product forms such as long fibers, short fibers, woven fabrics, knitted fabrics, nonwoven fabrics, felts, artificial leathers, and thermoformed products can be employed. In particular, in the case of general clothing, interior products, and wiping cloths, it is preferable to use a woven or knitted fabric. On the other hand, when used for functional products such as artificial leather or a filter, an adsorbing material, or a polishing cloth, a nonwoven fabric is preferable.
[0026]
As described above, the nanoporous fiber of the present invention can provide a high-quality dyed fabric that does not have a lowering of the coloring property as compared with the conventional porous fiber and that is excellent in hygroscopicity and adsorptivity. For this reason, it is not only used for comfortable clothing such as pantyhose, tights, inners, shirts, blousons, pants, and coats, but also clothing materials such as cups and pads, living materials such as wiping cloths, curtains, carpets, mats, furniture, etc. It can be suitably used for interior applications, industrial materials applications such as filters and polishing cloths, and vehicle interior applications such as car seats and ceiling materials. Furthermore, by adsorbing functional molecules, it can also be used as a cutting-edge material such as healthcare / cosmetics-related products, pharmaceutical fabrics, and electrodes for fuel cells, as well as medical and IT-related products.
[0027]
Although the method for producing the nanoporous fiber of the present invention is not particularly limited, it can be obtained, for example, by removing a readily soluble polymer from a polymer alloy fiber composed of a poorly soluble polymer and a readily soluble polymer as described below. .
[0028]
For example, when the hardly soluble polymer uses the sea-island structure polymer alloy fiber of the sea and the easily soluble polymer is an island, an island having a diameter of 200 nm or more, that is, an abundance ratio of the coarse aggregated polymer particles is an area ratio with respect to the entire island. It is preferably at most 3%. As a result, it is possible to remarkably reduce a decrease in color developability when a nanoporous fiber is used. Here, since the island may have a slightly distorted elliptical shape and is not always a perfect circle, the diameter is obtained by converting the island area into a circle. The area with respect to the entire island is the total area of all the islands existing in the fiber cross section, and can be estimated from the fiber cross section observation and the polymer blend ratio. The area ratio of the island having a diameter of 200 nm or more is preferably 1% or less. More preferably, the area ratio of the island having a diameter of 100 nm or more is 3% or less, and further preferably, the area ratio of the island having a diameter of 100 nm or less is 1% or less.
[0029]
Further, it is preferable that the average diameter of the islands is 1 to 100 nm, because removing the islands results in a nanoporous fiber having a smaller pore size than a conventional porous fiber. When the pore size is on the nanometer level, the scattering of visible light hardly occurs, so that not only the coloring property is remarkably improved, but also harmful ultraviolet rays are greatly scattered, and a new function of UV cutting is exhibited. Further, since the surface area is drastically increased, there is a great advantage that excellent hygroscopicity and adsorptivity, which could not be expected with conventional porous fibers, are exhibited. As described above, from the viewpoint of color development and adsorptivity, it is advantageous that the average diameter of the islands is small. However, if the average diameter is excessively small, the polymer interface becomes too large and the interaction here becomes excessive, resulting in a thinning in the melt spinning process. Behavior tends to be unstable. For this reason, the average diameter of the islands is more preferably 10 to 50 nm.
[0030]
Further, the islands preferably form a streak structure. Thereby, spinning thinning behavior can be stabilized. Here, the streak structure refers to an island having a length-to-diameter ratio of 4 or more in the fiber axis direction.
[0031]
Instead of a sea-island structure polymer alloy, an alloy fiber having the following special layer structure can be used. Here, the special layer structure indicates the following state when the fiber cross section is observed with a TEM. That is, the blended heterogeneous polymers are in a state of forming a layer and intermingling with each other (FIG. 14, TEM photograph of fiber cross section). For this reason, the interface between the different polymers is much larger than the sea-island structure (FIG. 3, TEM photograph of the fiber cross section), and the compatibility is improved as compared with the sea-island structure. This is a very unique structure having a lower compatibility than that of a so-called uniform structure. However, since a clear periodicity is not recognized in the layer, it is distinguished from a modulation structure by so-called spinodal decomposition. Here, the TEM sample is metal-stained, and the dark part is N6, which is a hardly soluble polymer, and the light part is copolymerized PET, which is a readily soluble polymer. In addition, it is clearly distinguished from a so-called sea-sea structure in that a layer is formed. The sea-sea structure is a very unstable structure that appears at a blend ratio near the sea / island reversal in the polymer blend, and it is naturally extremely difficult to perform stable spinning in this region. It is preferable that the thickness of one layer of the easily soluble component in the cross-sectional direction of the fiber be 1 to 100 nm, since the heterogeneous polymer is sufficiently ultrafinely dispersed and the performance of the blended polymer can be sufficiently exhibited even with a small amount of blend. This layer observed in the cross section of the fiber extends as a streak in the longitudinal direction of the fiber (FIG. 16, TEM photograph of the fiber longitudinal section).
[0032]
As described above, the nanoporous fiber of the present invention can be obtained by uniformly and ultrafinely dispersing the easily soluble polymer in the poorly soluble polymer, but the easily soluble polymer has a low melting point or a low softening point. Even if is used, there is an advantage that it is possible to improve the processability of the yarn processing such as crimping and twisting, which are performed at a high temperature, and the fabric processing, and also to improve the quality of the obtained product.
[0033]
In addition, the polymer type in the polymer alloy fiber may be at least two types having different solubility, and if necessary, the types of hardly soluble and easily soluble polymers can be increased, and a compatibilizer may be used in combination. Of course it is possible.
[0034]
In the above-mentioned polymer alloy fiber, the easily soluble polymer is preferably an alkali easily soluble polymer, because the porous treatment step for removing islands can utilize an alkali treatment step which is a post-processing step of a usual fiber. For example, when an organic solvent-soluble polymer such as polystyrene is used as the easily soluble polymer, there is a great merit considering that explosion-proof equipment is required. It is more preferable that the easily soluble polymer is a hot water soluble polymer because islands can be removed in the fiber scouring step. Examples of the alkali-soluble polymer include polyesters and polycarbonates, and examples of the hot water-soluble polymer include polyesters copolymerized with a large amount of a hydrophilic group, and alkylene oxides and polyvinyl alcohols, and modified products thereof. Can be.
[0035]
In order to maintain the mechanical properties of the nanoporous fiber of the present invention, the blend ratio of the hardly soluble polymer is preferably set to 40 to 95% by weight. The blend ratio of the poorly soluble polymer is more preferably 70 to 85% by weight.
[0036]
In addition, since the above-mentioned polymer alloy fibers do not contain coarse agglomerated polymer particles, spinning is more stable than in known techniques (Patent Literatures 1 to 4), and is characterized in that fibers with small yarn spots are easily obtained. Yarn spots can be evaluated in terms of Worcester spots (U%), but if the polymer alloy fibers used in the present invention have a U% of 0.1 to 5%, they can be used in textile products such as apparel, interiors, and vehicle interiors. In this case, a high-quality product with a small stain spot is obtained, which is preferable. U% is more preferably 0.1 to 2%, even more preferably 0.1 to 1.5%. In particular, in the case of producing a heather for apparel use, a thick thread having U% of 3 to 10% can be used.
[0037]
By setting the strength of the polymer alloy fiber to 2 cN / dtex or more, the processability in twisting, weaving, knitting and the like can be improved, which is preferable. The strength is preferably at least 3 cN / dtex. Further, if the elongation is 15 to 70%, the processability in twisting, weaving, knitting and the like can be improved, which is preferable. Further, when used as a raw yarn for drawing false twisting, the elongation is preferably 70 to 200% from the viewpoint of processability in false twisting. In the case of a raw yarn for drawing, the elongation is preferably about 70 to 500% from the viewpoint of processability in drawing.
[0038]
The method for producing the above-mentioned polymer alloy fiber is not particularly limited, but for example, the following method can be adopted.
[0039]
That is, the hardly soluble polymer and the easily soluble polymer are melt-kneaded to obtain a polymer alloy comprising the hardly soluble polymer and / or the easily soluble polymer in which the hardly soluble polymer and / or the easily soluble polymer is finely dispersed. Then, the polymer alloy fiber of the present invention can be obtained by melt-spinning this. Here, the melt kneading method is important, and the formation of coarse agglomerated polymer particles can be significantly suppressed by forcibly kneading with an extrusion kneader or a static kneader. In all of the known techniques (Patent Documents 1 to 4), since chip blends (dry blends) are used, the blend unevenness is large and aggregation of island polymers cannot be prevented.
[0040]
In the present invention, from the viewpoint of forcible kneading, it is preferable to use a twin-screw extruder as an extrusion kneader and to use a static kneader having a division number of 1,000,000 or more. Further, the method of supplying the kneaded polymer is preferable because the kneaded polymer is separately measured and supplied, thereby suppressing the blending unevenness and the variation of the blend ratio with time. At this time, they may be separately supplied as pellets, or may be separately supplied in a molten state. Further, two or more kinds of polymers may be supplied to the root of the extrusion kneader, or a side feed may be used in which one component is supplied from the middle of the extrusion kneader.
[0041]
When a twin-screw extrusion kneader is used as the kneading device, it is preferable to achieve both high kneading and suppression of the polymer residence time. The screw is composed of a feeding section and a kneading section, but it is preferable to set the length of the kneading section to 20% or more of the effective length of the screw so that high kneading can be achieved. Further, by setting the kneading part length to 40% or less of the effective screw length, excessive shear stress can be avoided, and the residence time can be shortened, thereby suppressing thermal degradation of the polymer and gelation of the polyamide component. Can be. In addition, by positioning the kneading section as far as possible on the discharge side of the twin-screw extruder, the residence time after kneading can be shortened, and reaggregation of the island polymer can be suppressed. In addition, when the kneading is strengthened, a screw having a backflow function for feeding the polymer in the reverse direction in the extrusion kneader can be provided.
[0042]
Furthermore, as a venting method, the decomposition gas during kneading is sucked, the hydrolysis of the polymer is suppressed by reducing the water content in the polymer, and the amount of amine terminal groups in polyamide and the amount of carboxylic acid terminal groups in polyester are also suppressed. Can be.
[0043]
Further, from the viewpoint of suppressing re-aggregation of the island polymer, the residence time from polymer alloy formation and melting to discharge from the spinneret is also important, and the time from the tip of the molten portion of the polymer alloy to discharge from the spinneret is 30 minutes. It is preferable to be within. In particular, in the case of an alloy of nylon and hydrophilic group-copolymerized PET, care must be taken because the hydrophilic group-copolymerized PET is likely to re-aggregate.
[0044]
Further, a combination of polymers is also important for miniaturization of the island diameter, and by increasing the affinity between the hardly soluble polymer and the easily soluble polymer, the easily soluble polymer which becomes an island can be easily microfinely dispersed. For example, when nylon is used as the poorly soluble polymer and polyethylene terephthalate (PET) is used as the easily soluble polymer, a hydrophilic group copolymerized PET obtained by copolymerizing PET with 5-sodium sulfoisophthalic acid (SSIA) as a hydrophilic component is used. When used, the affinity with nylon can be improved. In particular, it is preferable to use hydrophilic PET having an SSIA copolymerization ratio of 4 mol% or more. The melt viscosity ratio between the two is also important, and the greater the viscosity ratio of the sea polymer / island polymer, the greater the shearing force applied to the island polymer, and the more easily the islands are finely dispersed. However, an excessively large viscosity ratio causes kneading unevenness and deterioration of spinnability. Therefore, the viscosity ratio is preferably about 1/10 to 2.
[0045]
Due to the characteristics of the production method as described above, the generation of coarse aggregated polymer particles is suppressed, so that the viscoelastic balance of the polymer alloy is less likely to be disrupted and the spinning discharge is stable as compared with the known techniques (Patent Documents 1 to 4). There is also an advantage that spinnability and thread spots can be significantly improved. Furthermore, if the diameter of the die hole is larger than usual, the shear stress to the polymer alloy in the die hole can be reduced and the viscoelastic balance can be maintained, so that the spinning stability is improved. Specifically, it is preferable to use a die capable of reducing the ejection linear velocity of the die of the polymer alloy to 15 m / min or less. In addition, the cooling of the yarn is also important, and the distance from the die to the active cooling start position is set to 1 to 15 cm. It can be stabilized.
[0046]
From the viewpoint of miniaturizing the island polymer, the spinning draft is preferably 100 or more. Further, in order to suppress changes with time of the dimensions and physical properties of the undrawn yarn, the spinning speed is preferably 2500 m / min or more to develop the fiber structure.
[0047]
FIG. 5 shows an example of a nanoporous fiber produced from the above-mentioned polymer alloy fiber. The density of the metal dye is finer than that of the precursor polymer alloy fiber (FIG. 3). It can be seen that the trace from which was removed is crushed. Here, the dark portion indicates the N6 high density region, and the light portion indicates the N6 low density region. Here, the light portion is considered to correspond to the pore. That is, there is an advantage that the pore size can be made smaller than the dispersion size of the easily soluble polymer in the polymer alloy stage. In addition, not only the pores but also the fiber diameter itself may shrink with the removal of the easily soluble polymer. Further, FIG. 6 shows the fiber longitudinal section of this nanoporous fiber. In the case of the polymer alloy fiber, the easily soluble polymer extended in a streak shape (FIG. 4), but in the case of the nanoporous fiber, the streak was partially broken and a granular light and shade pattern was shown. It turns out that there is.
[0048]
As described above, the nanoporous fiber of the present invention can be obtained by using the polymer alloy fiber obtained by a manufacturing method different from the conventional one, which has a smaller pore size than the conventional one, and a coarse pore size. It is an excellent material that contains almost no and is applicable not only to clothing but also to various fields.
[0049]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. In addition, the following method was used for the measuring method in an Example.
[0050]
A. Polymer melt viscosity
The melt viscosity of the polymer was measured by Capillograph 1B manufactured by Toyo Seiki. In addition, the storage time of the polymer from the sample introduction to the measurement start was 10 minutes.
[0051]
B. Relative viscosity of nylon
Nylon pellets were dissolved in a 98% sulfuric acid solution to adjust the concentration to 0.01 mg / ml, and then measured at 25 ° C.
[0052]
C. Intrinsic viscosity of polyester [η]
Measured in orthochlorophenol at 25 ° C.
[0053]
D. Melting point
Using Perkin Elmaer DSC-7, the peak top temperature indicating the melting of the polymer at 2nd run was defined as the melting point of the polymer. At this time, the heating rate was 16 ° C./min, and the sample amount was 10 mg.
[0054]
E. FIG. Mechanical properties
At room temperature (25 ° C.), the load-elongation curve was determined under the conditions shown in JIS L1013, with the pulling rate = 100% / min. Next, the load value at break was divided by the initial fineness, which was taken as the strength, and the elongation at break was divided by the initial sample length, and the elongation curve was determined as the elongation.
[0055]
F. Worcester spots of polymer alloy fiber (U%)
The measurement was performed in a normal mode at a yarn feeding speed of 200 m / min using USTER TESTER 4 manufactured by Zellbeger Worcester Co., Ltd.
[0056]
G. FIG. Heat shrinkage
Heat shrinkage (%) = [(L0−L1) / L0)] × 100 (%)
L0: Original length of the skein measured by skewing the drawn yarn and measuring the initial load at 0.09 cN / dtex
L1: The skein whose L0 was measured was treated in boiling water for 15 minutes in a substantially load-free state, and after air-drying, the skein length under an initial load of 0.09 cN / dtex
H. Fiber cross section observation by TEM
Ultra-thin sections were cut out in the cross-sectional direction or the longitudinal cross-sectional direction of the fiber, and the cross section of the fiber was observed with a transmission electron microscope (TEM). In addition, metal staining was performed as necessary.
[0057]
TEM equipment: Model H-7100FA manufactured by Hitachi, Ltd.
I. Pore diameter or island polymer diameter
The pore diameter is determined as follows. That is, the diameter of the island in terms of the circle was determined from the photograph of the fiber cross-section by TEM using image processing software (WINROOF). In addition, when it was too fine or the shape was complicated and analysis by WINROOF was difficult, the analysis was carried out visually and manually. The average diameter was determined by their simple number average. At this time, 300 or more randomly selected pores in the same cross section were used as the average pores. However, since the sample for TEM observation is an ultrathin section, the sample is liable to be broken or perforated. For this reason, the diameter analysis was performed carefully while checking the conditions of the sample. In addition, the inorganic fine particles and voids around them were not included in the pores. The island polymer diameter was based on the pore diameter analysis.
[0058]
J. Color development evaluation
The obtained sample was stained according to a conventional method, and the color development with a comparative sample stained under the same conditions was compared. As a comparative sample, a polymer formed of a nanoporous fiber by a conventional method was used. More specifically, the following method was used.
[0059]
In the case of nylon, "Nylosan Blue N-GFL" manufactured by Clariant Japan Co., Ltd. is used as the dye, and this dye is 0.8% by weight of the fiber product, a dyeing solution adjusted to pH 5 at a bath ratio of 100 times, 90 ° C. × Treated for 40 minutes.
[0060]
In the case of polyester, "ForonNavy S-2GL" manufactured by Clariant Japan Co., Ltd. is used as a dye, and the dye is 0.8% by weight of a fiber product and a dyeing solution adjusted to pH 5 at a bath ratio of 1: 100 at 130 ° C. (Polylactic acid was 110 ° C.) for 40 minutes.
[0061]
In the visual judgment, those which obtained color development properties higher than or almost equal to the comparison (◎) were slightly inferior to the comparison but were sufficient for clothing (○), and those which were inferior were rejected. (△, ×).
[0062]
K. Moisture absorption (ΔMR)
A sample is weighed in a weighing bottle in an amount of about 1 to 2 g, kept at 110 ° C. for 2 hours, dried and weighed (W0). Then, the target substance is kept at 20 ° C. and a relative humidity of 65% for 24 hours and then weighed. (W65). Then, it is kept at 30 ° C. and a relative humidity of 90% for 24 hours, and then its weight is measured (W90). Then, calculation is performed according to the following equation.
[0063]
MR65 = [(W65−W0) / W0] × 100% (1)
MR90 = [(W90−W0) / W0] × 100% (2)
ΔMR = MR90-MR65 (3)
L. Reversible water swellability and swelling ratio in the yarn longitudinal direction
After drying the fiber at 60 ° C. for 4 hours, the original length (L0 ′) is measured. Then, the fiber is immersed in water at 25 ° C. for 10 minutes, taken out of the water and quickly measured for the length after treatment (L1 ′). Further, after drying the fiber at 60 ° C. for 4 hours, the length after drying (L2 ′) is measured. Then, drying / water immersion is repeated three times, and if the swelling ratio in the third yarn longitudinal direction is 50% or more of the swelling ratio in the first yarn longitudinal direction, it has reversible water swellability. did. The swelling ratio in the longitudinal direction of the yarn was calculated as follows. The length of the fiber was measured by connecting a colored yarn to two places of the fiber and measuring the distance between them. This distance was set to be about 100 mm.
[0064]
Swelling ratio (%) in the yarn longitudinal direction = ((L1′−L0 ′) / L0 ′) × 100 (%)
M. Crimp characteristics, CR value of false twisted yarn
The false twisted yarn was removed, treated for 15 minutes in boiling water in a substantially load-free state, and air-dried for 24 hours. The sample was immersed in water under a load equivalent to 0.088 cN / dtex (0.1 gf / d), and the skein length L0 ″ was measured after 2 minutes. Next, a load equivalent to 0.088 cN / dtex in water was measured. Was replaced with a slight load equivalent to 0.0018 cN / dtex (2 mgf / d), and the skein length L1 ″ after 2 minutes was measured. Then, the CR value was calculated by the following equation.
[0065]
CR (%) = [(L0 ″ −L1 ″) / L0 ″] × 100 (%)
Example 1
Relative viscosity 2.15, melt viscosity 274 poise (280 ° C., shear rate 2432 sec. ^-1 ), N6 (80% by weight) having a melting point of 220 ° C., an intrinsic viscosity of 0.60, and a melt viscosity of 1400 poise (280 ° C., a shear rate of 2432 sec.) ^-1 ), 5 mol% of 5-sodium sulfoisophthalic acid having a melting point of 250 ° C., and copolymerized PET (20% by weight) were melt-kneaded at 260 ° C. with a twin-screw extruder to obtain a polymer alloy chip. The kneading conditions at this time were as follows.
[0066]

[0067]

[0068]

The copolymer PET contained 0.05% by weight of titanium oxide. Then, this polymer alloy was melted in a melting section 2 at 270 ° C., and was led to a spin block at a spinning temperature of 275 ° C. Then, the polymer alloy melt was filtered with a metal nonwoven fabric having a critical filtration diameter of 15 μm, and then melt-spun (FIG. 23). At this time, the residence time from the melting part 2 to the discharge was 10 minutes. As shown in FIG. 24, a die having a measuring part 11 having a diameter of 0.2 mm above the discharge hole, having a discharge hole diameter 13 of 0.5 mm and a discharge hole length 12 of 1.25 mm was used. At this time, the discharge rate per single hole was 2.1 g / min, and the die discharge linear velocity of the polymer alloy was 10 m / min. The distance from the lower surface of the base to the cooling start point (upper end of the chimney 5) was 9 cm. The discharged yarn is cooled and solidified for 1 m by a cooling wind of 20 ° C., and after being refueled by a refueling guide 7 installed 1.8 m below the base 4, a first heating roller 8 and a second heating roller 8 which are not heated. 9 at 3800 m / min. The spinnability at this time was good, and the breakage during continuous spinning for 24 hours was zero. Further, there was no package collapse due to swelling of the wound package with time, which is a problem with nylon, and the handleability was excellent. Then, this was subjected to stretch false twisting using the apparatus shown in FIG. At this time, the stretching ratio was 1.3 times, the temperature of the heater 23 was 165 ° C., the urethane disk triaxial twister was used as the rotor 25, and the D / Y ratio was 1.65. The obtained 50-dtex, 12-filament false twisted yarn exhibited excellent physical properties such as a strength of 3.5 cN / dtex, an elongation of 29%, a heat shrinkage of 8%, and a CR of 38% (Table 2). Further, when the cross section of the obtained polymer alloy crimped yarn was observed with a TEM, N6 showed a sea-island structure (dark portion) and copolymerized PET showed a sea-island structure (island) (FIG. 2). A polymer alloy fiber having a diameter of 25 nm and ultrafine dispersion of copolymerized PET was obtained. The area ratio of the island having a diameter of 200 nm or more to the whole island was 0.1% or less, and the area ratio of the island having a diameter of 100 nm or more was 0.9%. Here, the area ratio with respect to the entire island refers to the ratio of the area of the island component to the total area, and is a measure of the coarse aggregated polymer. Further, it was found from the fiber longitudinal section TEM observation that the islands formed a streak structure.
[0069]
Circular knitting was prepared as this polymer alloy crimped yarn S twist / Z twist twin yarn and immersed in a 3% sodium hydroxide aqueous solution (90 ° C., bath ratio 1: 100) for 1 hour to obtain a polymer alloy fiber. 99% or more of the copolymerized PET was removed by hydrolysis. Then, it was washed with water and dried. Thus, a circular knit made of N6 nanoporous fiber was obtained.
[0070]
When the cross section of the fiber of this N6 nanoporous fiber was observed by TEM (FIG. 1), there were no coarse pores having a diameter of 50 nm or more, and the average diameter of the pores was 25 nm. Here, the dark portion corresponds to the N6 polymer, and the thin portion corresponds to the pores, but the pores were found to be independent pores.
[0071]
In addition, the circular knit made of the N6 nanoporous fiber was dyed and evaluated for color development. The color development was excellent. Further, when the moisture absorption rate (ΔMR) of this was measured, it was 5.6%, showing an excellent moisture absorption property exceeding cotton. Further, it exhibited reversible water swelling, and the yarn extracted from the circular knit made of this N6 nanoporous fiber set at 180 ° C. for 1 minute had a swelling ratio in the yarn longitudinal direction of 7%. Further, when the mechanical properties were measured, the strength was 2.6 cN / dtex and the elongation was 30%, indicating sufficient mechanical properties as a fiber product. Table 1 shows the physical properties of the N6 nanoporous fiber.
[0072]
Example 2
N6 was melted at 1260 poise (280 ° C., shear rate 2432 sec. ^-1 The melt spinning and draw false twist were performed in the same manner as in Example 1 except that the melt viscosity ratio was changed as shown in Table 2 using N6). At this time, the discharge rate per single hole and the number of holes were changed to obtain a polymer alloy crimped yarn having 105 dtex, 96 filaments, strength of 3.8 cN / dtex, elongation of 29%, heat shrinkage of 8%, and CR of 35%. (Table 2). As a result of observing the cross section of the fiber of the obtained polymer alloy crimped yarn with a TEM, the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles was 0.1% or less, and the diameter was 100 nm or more. Was also 0.1% or less. Further, it was found from the fiber longitudinal section TEM observation that the islands formed a streak structure.
[0073]
After circular knitting as in Example 1 as this polymer alloy crimped yarn S twist / Z twist twin yarn, 99% or more of the copolymerized PET was removed by an alkali treatment to obtain a circular knit made of N6 nanoporous fiber.
[0074]
As a result of observing the cross section of the fiber of this N6 nanoporous fiber with a TEM, the average diameter of the pores at the trace of the island polymer was 20 nm, and there were no large pores having a diameter of 50 nm or more. These pores were independent pores.
[0075]
In addition, the circular knit made of the N6 nanoporous fiber was dyed and evaluated for color development. The color development was excellent. The N6 nanoporous fiber had excellent physical properties as shown in Table 1.
[0076]
Example 3
Using the polymer alloy chip obtained in Example 1, melt spinning was carried out in the same manner as in Example 1, except that the discharge rate and the number of holes were changed, and the spinning speed was 900 m / min. At this time, the residence time from the melting part 2 to the discharge was 12 minutes. The spinnability was good, with no breakage during 24 hours of continuous spinning. Further, there was no package collapse due to swelling of the wound package with time, which is a problem with nylon, and the handleability was excellent. This was subjected to stretching heat treatment at a temperature of the first hot roller 16 of 70 ° C. and a temperature of the second hot roller 17 of 130 ° C. (FIG. 25). At this time, the stretching ratio between the first hot roller 16 and the second hot roller 17 was set to 3.2 times. The obtained polymer alloy fiber exhibited excellent properties of 70 dtex, 34 filaments, strength of 3.7 cN / dtex, elongation of 47%, U% = 1.2%, and heat shrinkage of 11%. Also, when the cross section of the obtained polymer alloy fiber was observed by TEM, N6 showed a sea-island structure (dark part) and copolymerized PET showed a sea-island structure (island) (FIG. 3). A polymer alloy fiber having a diameter of 38 nm and ultra-dispersed copolymerized PET was obtained. The islands having a diameter of 200 nm or more accounted for 1.2% of the area of the entire island. A cross-sectional TEM photograph of the melt-kneaded polymer alloy chip is shown in FIG. 7, where the island polymer is ultrafinely dispersed to a particle size of 20 to 30 nm, and is equal to or smaller than the island polymer diameter in the fiber cross section (FIG. 3). there were. The polymer is stretched to about 500 times through the drawing from the discharge of the die, and the island polymer diameter should be reduced to 1/22 or less of that in the polymer alloy in the fiber cross section. The fact that the diameter of the island polymer is larger indicates that the island polymer has re-agglomerated from the melting of the polymer alloy to the discharge of the die. It can be seen that it is important to appropriately select spinning conditions as in this example. Table 2 shows the physical properties of the polymer alloy fibers. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure.
[0077]
Circular knitting is prepared using the polymer alloy fiber obtained here, and this is immersed in a 3% aqueous sodium hydroxide solution (90 ° C., bath ratio 1: 100) for 1 hour to copolymerize the polymer alloy fiber. More than 99% of PET was hydrolyzed and removed. Then, it was washed with water and dried.
[0078]
When the fiber side surface of this N6 nanoporous fiber was observed with an optical microscope, the fiber diameter was slightly reduced as compared with the fiber before the alkali treatment, and it was found that shrinkage occurred in the fiber radial direction by removing the island polymer. Do you get it. Next, when the side surface of the fiber was observed with a SEM, at a magnification of about 2000 times, no irregularities were observed on the fiber surface, and the surface was clean. The cross section of the fiber of this N6 nanoporous fiber was observed with a TEM (FIG. 5). As a result, the density unevenness due to metal staining was finer than that of the original polymer alloy fiber (FIG. 3). Here, the dark part is the N6 high density part, and the light part is the N6 low density part. It is considered that the light portion corresponds to the pore. That is, by removing the island polymer, the pore size became finer than the original island polymer, the average diameter of the pores was 15 nm, and there were no coarse pores having a diameter of 50 nm or more. In addition, when the longitudinal section of the fiber was observed, the copolymerized PET was stretched in a streak form in the original polymer alloy (FIG. 4), whereas a light granular part was observed in the N6 nanoporous fiber (FIG. 6). 5 and 6, these pores were determined to be independent pores.
[0079]
In addition, the circular knit made of the N6 nanoporous fiber was dyed and evaluated for color development. The color development was excellent. Further, when the moisture absorption rate (ΔMR) of this was measured, it was 6%, showing excellent moisture absorption properties exceeding cotton. When the mechanical properties of the N6 nanoporous fiber were measured, the strength was 2.0 cN / dtex, and the elongation was 70%, indicating sufficient mechanical properties as a fiber product. Further, it exhibited reversible water swelling, and the yarn extracted from the circular knit made of this N6 nanoporous fiber set at 180 ° C. for 1 minute had a swelling ratio in the yarn longitudinal direction of 7%. Table 1 shows the physical properties of the N6 nanoporous fiber.
[0080]
Examples 4 and 5
N6 is melt viscosity 1260 poise or 1540 poise (280 ° C., shear rate 2432 sec. ^-1 ) Of N3 having a higher viscosity than that used in Example 3), and changing the melt viscosity ratio of N6 and the copolymerized PET as shown in Table 2, and performing melt spinning, drawing and heat treatment in the same manner as in Example 3. went. At this time, the amount of discharge per single hole and the number of holes were changed to obtain a polymer alloy fiber of 105 dtex and 96 filaments. The spinnability was good in each case, and the breakage during continuous spinning for 24 hours was zero. None of the obtained polymer alloy fibers contained coarse aggregated polymer particles, and islands having a diameter of 200 nm or more were 0.1% or less in area ratio to the whole islands, and islands having a diameter of 100 nm or more were 0.1% in area ratio. % Or less. Further, the yarn physical properties were excellent as shown in Table 2. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure.
[0081]
After circular knitting of these polymer alloy fibers in the same manner as in Example 3, 99% or more of the copolymerized PET was removed by alkali treatment to obtain a circular knit consisting of N6 nanoporous fibers.
[0082]
Observation of this N6 nanoporous fiber with an optical microscope and SEM revealed that, as in Example 3, shrinkage occurred in the fiber radial direction due to the removal of the island polymer, and at a magnification of about 2000, no irregularities were observed on the fiber surface and the surface was clean. When the cross section of the fiber of this N6 nanoporous fiber was observed by TEM, the density spots due to metal staining became finer than the original polymer alloy fiber, and the pore size became finer than the original island polymer by removing the island polymer. The average diameter of the pores was 15 nm, and there were no large pores having a diameter of 50 nm or more. When the longitudinal section of the fiber was observed, it was found to be a pattern in which granular shades were arranged in a cylindrical shape. From the above TEM observation, these pores were determined to be independent pores.
[0083]
In addition, the circular knit made of the N6 nanoporous fiber was dyed and evaluated for color development. The color development was excellent. The N6 nanoporous fiber had excellent physical properties as shown in Table 1.
[0084]
Example 6
Melt spinning, drawing and heat treatment were performed in the same manner as in Example 3 except that the blending ratio of N6 and the copolymerized PET was 50% by weight / 50% by weight, and the discharge amount per hole and the number of holes were changed. Was obtained. The spinnability was good, with no breakage during 24 hours of continuous spinning. FIG. 8 shows the fiber cross section of the obtained polymer alloy fiber observed by TEM. As shown in FIG. Of the islands having a diameter of 200 nm or more with respect to the entire islands and containing no coarse aggregated polymer particles, and the area ratio of the islands having a diameter of 100 nm or more was 0.1% or less. Was. Further, the yarn physical properties were excellent as shown in Table 2. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure.
[0085]
After circular knitting of the polymer alloy fiber in the same manner as in Example 3, 99% or more of the copolymerized PET was removed by an alkali treatment to obtain a circular knit made of N6 nanoporous fiber.
[0086]
FIG. 9 shows the results of TEM observation of the cross section of the N6 nanoporous fiber. The average diameter of the pores was 20 nm, and there were no large pores having a diameter of 50 nm or more. From FIG. 9, it was found that these pores were independent pores.
[0087]
In addition, the circular knit made of the N6 nanoporous fiber was dyed and evaluated for color development. The color development was excellent. The N6 nanoporous fiber had excellent physical properties as shown in Table 1.
[0088]
Example 7
N6 (50% by weight) used in Example 3 and PET (50% by weight) obtained by copolymerizing 12 mol% of 5-sodium sulfoisophthalic acid and 26 mol% of isophthalic acid were kneaded at 245 ° C. by a twin-screw extruder. Thus, a polymer alloy chip was obtained. This polymer alloy was melted at a spinning temperature of 250 ° C., the die diameter was set to 0.6 mm, the melt spinning was performed in the same manner as in Example 3 except that the discharge amount per single hole was changed, and the undrawn yarn was spun at a spinning speed of 800 m / min. Wound up. This was subjected to stretching heat treatment at a stretching ratio of 3.4 times, a first hot roller temperature of 90 ° C, and a second hot roller temperature of 130 ° C. As a result, a polymer alloy yarn of 85 dtex and 36 filaments was obtained. The spinnability was good, with no breakage during 24 hours of continuous spinning. The observation result of the fiber cross section of the obtained polymer alloy fiber by TEM is shown in FIG. 10, and the copolymerized PET exists as a layered island having a short axis of about 10 to 30 nm and a long axis of about 50 to 100 nm, The area ratio of the island having a diameter of 200 nm or more to the entire island without containing the aggregated polymer particles was 0.1% or less, and the area ratio of the island having a diameter of 100 nm or more was 0.1% or less. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. Further, the yarn physical properties were excellent as shown in Table 2.
[0089]
This polymer alloy fiber is circular knitted in the same manner as in Example 3, and then treated with a 3% by weight aqueous solution of sodium hydroxide (90 ° C., bath ratio 1:50) for 1 hour to dissolve 99% or more of the copolymerized PET. It was removed to obtain a circular knit made of N6 nanoporous fiber. At this time, remarkable shrinkage of the fiber in the radial direction was observed (the radial shrinkage was about 22%, and the cross-sectional area shrinkage was about 40%). The fiber side surface of the nylon 6 yarn after dissolution and removal was observed by SEM (× 2000), but no so-called streak-like grooves or voids, which were traces from which the copolymerized PET was removed, could not be observed.
[0090]
FIG. 11 shows the result of TEM observation of the cross section of the N6 nanoporous fiber. The average diameter of the pores was 10 nm, and there were no large pores having a diameter of 50 nm or more.
[0091]
In addition, the circular knit made of the N6 nanoporous fiber was dyed and evaluated for color development. The color development was excellent. Further, when the swellability of the N6 nanoporous fiber with water was measured, the swelling ratio in the yarn longitudinal direction showed a large value of 11.1%. In the third measurement, the swelling ratio in the yarn longitudinal direction was hardly reduced, and both reversibility and durability were sufficient. After heat treatment of the circular knit at 140 ° C. for 30 minutes, the swellability of the N6 nanoporous fiber with water was measured. The swelling ratio in the yarn longitudinal direction was 7.3%, but the swelling ratio was lower than before the heat treatment. The value was much larger than that of 3% of the normal N6 fiber. This indicates that the swelling ratio in the yarn longitudinal direction can be controlled by the heat treatment, which is an advantage that the fabric can be easily designed. The N6 nanoporous fiber had excellent physical properties as shown in Table 1.
[0092]
Example 8
The copolymerized PET was obtained by copolymerizing 7 mol% of isophthalic acid and 4 mol% of bisphenol A ethylene oxide adduct (melting point: 225 ° C., containing 0.05% by weight of titanium oxide). Melt spinning, stretching and heat treatment were carried out in the same manner as in Example 3 except that the die diameter was 50% by weight / 50% by weight and the die hole diameter was 0.7 mm. Although not insignificant, the spinning became unstable compared to Example 3, and the number of yarn breaks during continuous spinning for 24 hours was two. FIG. 12 shows the results of TEM observation of the fiber cross section of the obtained polymer alloy fiber. Although the number of coarse agglomerated polymer particles was small, the average diameter of the islands was 143 nm, and the whole of the islands having a diameter of 200 nm or more. Was 5%. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. The yarn properties are shown in Table 2.
[0093]
After circular knitting of the polymer alloy fiber in the same manner as in Example 3, 99% or more of the copolymerized PET was removed by an alkali treatment to obtain a circular knit made of N6 nanoporous fiber.
[0094]
When this N6 nanoporous fiber was observed with an optical microscope, shrinkage was observed in the fiber radial direction due to the removal of the island polymer as in Example 1. FIG. 13 shows the result of observing the cross section of the fiber of this N6 nanoporous fiber with a TEM. The trace of the island polymer coming out is crushed into pores having a width of about 10 to 30 nm and a length of about 100 nm. Large pores of 50 to 100 nm were also found. However, the area ratio of the coarse pores having a diameter of 200 nm or more was 0.5%. The color development was evaluated, and the color development was inferior to that of Example 3, but at a level usable for clothing. These pores were independent pores.
[0095]
Example 9
Instead of copolymerized PET, a hot water-soluble polymer of a polyalkylene oxide derivative, "PAOGEN PP-15" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was used. The discharge amount per hole and the number of holes were changed, and the spinning speed was 4000 m / m. The melt spinning, stretching and heat treatment were performed in the same manner as in Example 3 except that the draw ratio was set to 1.2 times, to obtain a polymer alloy fiber of 55 dtex and 68 filaments. The spinnability was good, with no breakage during 24 hours of continuous spinning. As a result of observing the fiber cross section of the obtained polymer alloy fiber with a TEM, it was found that the area ratio of the island having a diameter of 200 nm or more to the whole island without coarse aggregated polymer particles was 1.3%. Further, the yarn physical properties were excellent as shown in Table 2.
[0096]
After circular knitting of this polymer alloy fiber in the same manner as in Example 3, it was treated with hot water at 100 ° C. for 2 hours to remove 99% or more of the hot water-soluble polymer to obtain a circular knit made of N6 nanoporous fiber.
[0097]
As a result of observing the cross section of the fiber of this N6 nanoporous fiber with a TEM, the average diameter of the pores was 30 nm, and there were no large pores having a diameter of 50 nm or more. These pores were independent pores.
[0098]
In addition, the circular knit made of the N6 nanoporous fiber was dyed and evaluated for color development. The color development was excellent. The N6 nanoporous fiber had excellent physical properties as shown in Table 1.
[0099]
Example 10
Instead of copolymerized PET, a weight average molecular weight of 150,000 and a melt viscosity of 857 poise (240 ° C., 2432 sec.) ^-1 ), Using a poly-L-lactic acid having a melting point of 170 ° C. (optical purity of 99.5% or more) and kneading at 220 ° C. in the same manner as in Example 1. The weight average molecular weight of polylactic acid was determined as follows. THF (tetrohydrofuran) was mixed with a chloroform solution of the sample to prepare a measurement solution. This was measured at 25 ° C. using Gels Permeation Chromatography (GPC) Waters 2690 manufactured by Waters, and the weight average molecular weight was calculated in terms of polystyrene. Note that N6 used in Example 1 was 240 ° C. and 2432 sec. ^-1 ) Was 570 poise. Melt spinning was performed in the same manner as in Example 1 except that the discharge amount per single hole and the number of die holes were changed, and the spinning speed was set to 3500 m / min, 105 dtex, 36 filaments, strength 3.1 cN / dtex, elongation 107%, A highly oriented undrawn yarn of U% 1.2% was obtained. The spinnability was good, with no breakage during 24 hours of continuous spinning. This was subjected to stretch false twisting in the same manner as in Example 1 except that the draw ratio was set to 1.4, and 76 dtex, 36 filaments, strength 4.0 cN / dtex, elongation 29%, U% 1.3%, CR 35% A false twisted yarn was obtained. At this time, in consideration of the melting point of the poly-L-lactic acid, the heater temperature was set to 160 ° C., so that a false-twisted yarn excellent in quality with almost no untwisting was obtained, and the processability in drawing false-twisting was good. there were. As a result of observing the cross section of the fiber of the obtained polymer alloy crimped fiber with a TEM, the area ratio of the island polymer having a diameter of 200 nm or more to the entire island component, which does not contain coarse aggregated polymer particles, is 0.1% or less. Had an average diameter of 80 nm. In addition, the yarn properties were excellent as shown in Table 1.
[0100]
This polymer alloy crimped yarn was circularly knitted in the same manner as in Example 1 and then subjected to an alkali treatment to remove 99% or more of the poly-L-lactic acid to obtain a circular knitted fiber composed of N6 nanoporous fibers. In addition, the circular knit made of the N6 nanoporous fiber was dyed and evaluated for color development. The color development was excellent.
[0101]
The N6 nanoporous fiber was pulled out from the circular knitting, and the cross section of the fiber was observed by TEM. Was. Further, the strength of the obtained nanoporous fiber was higher than that of Example 1. This is because sulfonic acid groups contained in the copolymerized PET used in Example 1 generate a pseudo-crosslinked structure and tend to inhibit the formation of a fiber structure of N6, whereas PLA has less such adverse effects. it is conceivable that.
[0102]
Example 11
The N6 and copolymerized PET used in Example 3 were melted at 270 ° C. and 290 ° C. respectively using the apparatus shown in FIG. 26, and then the static kneader 20 (“High Mixer” 10 manufactured by Toray Engineering Co., Ltd.) installed in the pack 3 was used. ), And mixed. Then, this was filtered through a metal nonwoven fabric filter having an absolute filtration diameter of 20 μm, and then discharged from a die having a hole diameter of 0.35 mm. At this time, the spinning temperature was 280 ° C., and the distance from the die 4 to the upper end of the chimney 5 was 7 cm. This was taken up at a spinning speed of 900 m / min and wound up through a second take-up roller 9. Spinning was performed for 24 hours, but there was no yarn breakage during spinning, indicating good spinnability. This was stretched and heat-treated using the apparatus of FIG. At this time, the stretching ratio was 3.2 times, the temperature of the first hot roller 16 was 70 ° C., and the temperature of the second hot roller 17 was 130 ° C. There was no yarn breakage during stretching and heat treatment, indicating good stretchability.
[0103]
As a result, a polymer alloy fiber of 56 dtex and 12 filaments was obtained, and the U% was 1.5%, which was sufficiently small. When the cross section of the fiber was observed with a TEM, the N6 part and the light PET part which were deeply dyed by metal dyeing formed a special layer structure, and the thickness of the PET layer part was about 20 nm (about 20 nm) ( (FIG. 14). In addition, this fiber had a sea-island structure in which the special layer structure collapsed from the fiber surface layer to about 150 nm, but when the area of the special layer structure portion was estimated, it was 98% of the entire fiber cross section, Most of the fiber cross section formed a special layer structure (FIG. 15). When the longitudinal section of this polymer alloy fiber was observed by TEM, the layer was streaked (FIG. 16).
[0104]
Circular knitting was made using this polymer alloy fiber, but there was no trouble in the knitting process, and good processability was shown. The circular knit was further immersed in a 3% aqueous solution of sodium hydroxide at 95 ° C. for 1 hour to completely remove PET from the polymer alloy fiber, thereby obtaining a circular knit composed of N6 nanoporous fibers. This circular knitting showed ΔMR = 5.7%, showing excellent hygroscopicity exceeding cotton. The cross section of the fiber of this nanoporous fiber was observed with a TEM (FIG. 17). As a result, the density unevenness due to metal staining was finer than that of the original polymer alloy fiber. Here, the dark part is the N6 high density part, and the light part is the N6 low density part. It is considered that the light portion corresponds to the pore. When the longitudinal section of the fiber was observed, PET was stretched in a streak shape in the original polymer alloy (FIG. 16), whereas a light granular portion was observed in the nanoporous fiber (FIG. 18), and the pores were crushed. It was suggested that. There were no large pores having a diameter of 50 nm or more.
[0105]
In addition, the circular knit made of the N6 nanoporous fiber was dyed and evaluated for color development. The color development was excellent. The N6 nanoporous fiber had excellent physical properties as shown in Table 1.
[0106]
Example 12
Melt spinning was carried out in the same manner as in the example, except that the N6 / copolymerized PET blend ratio was 50% by weight / 50% by weight. The spinnability was good, and the yarn breakage was zero after 24 hours of spinning. This was stretched and heat-treated using the apparatus of FIG. At this time, the stretching ratio was 3.2 times, the temperature of the first hot roller 16 was 70 ° C., and the temperature of the second hot roller 17 was 130 ° C. There was no yarn breakage during stretching and heat treatment, indicating good stretchability.
[0107]
FIG. 19 shows the results of TEM observation of the fiber cross section of the obtained polymer alloy fiber. As shown in FIG. 19, the copolymerized PET exists as rosary islands in which fine islands having a diameter of about 10 to 20 nm are connected. The area ratio of an island having a diameter of 200 nm or more to the entire island without polymer particles was 0.1% or less, and the area ratio of an island having a diameter of 100 nm or more was 0.1% or less. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. Further, the yarn physical properties were excellent as shown in Table 2.
[0108]
After circular knitting of the polymer alloy fiber in the same manner as in Example 3, 99% or more of the copolymerized PET was removed by an alkali treatment to obtain a circular knit made of N6 nanoporous fiber.
[0109]
The results of TEM observation of the cross section of the N6 nanoporous fiber are shown in FIG. 20, indicating a fine shading pattern of about 10 to 20 nm, suggesting that many pores having a diameter of 20 nm or less exist. In addition, there were no large pores having a diameter of 50 nm or more.
[0110]
In addition, the circular knit made of the N6 nanoporous fiber was dyed and evaluated for color development. The color development was excellent. The N6 nanoporous fiber had excellent physical properties as shown in Table 1.
[0111]
Example 13
Melt spinning, stretching and heat treatment were performed in the same manner as in Example 12, except that N6 was set to N66. At this time, the spinning temperature was 280 ° C., and the blend ratio of N66 / copolymerized PET was 80% by weight / 20% by weight. The spinnability was good, with no breakage during 24 hours of continuous spinning. As a result of observing the cross-section of the obtained polymer alloy fiber with a TEM, the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles is 0.1% or less, and the area ratio of the island is 100 nm or more. Was also 0.1% or less. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. Further, the yarn physical properties were excellent as shown in Table 2.
[0112]
After circular knitting of the polymer alloy fiber in the same manner as in Example 3, 99% or more of the copolymerized PET was removed by an alkali treatment to obtain a circular knit made of N6 nanoporous fiber.
[0113]
As a result of observing the cross section of the fiber of this N66 nanoporous fiber by TEM, the average diameter of the pores was 20 nm, and there were no large pores having a diameter of 50 nm or more.
[0114]
In addition, the circular knit made of this N66 nanoporous fiber was dyed and evaluated for color development. The color development was excellent. The N66 nanoporous fiber had excellent physical properties as shown in Table 1.
[0115]
Example 14
Melt spinning was performed in the same manner as in Example 1, and direct spinning was performed using the apparatus shown in FIG. At this time, the discharge amount per single hole and the number of die holes were changed, and the peripheral speed of the first hot roller 28 was 2000 m / min, the temperature was 40 ° C., the peripheral speed of the second hot roller 29 was 4500 m / min, and the temperature was 150 ° C. and 55 dtex. , 12 filaments, a strength of 4.4 cN / dtex, an elongation of 37%, a U% of 1.2% and a heat shrinkage of 12% were obtained. The spinnability was good, and the yarn breakage was zero after 24 hours of spinning. None of the obtained polymer alloy fibers contained coarse aggregated polymer particles, and islands having a diameter of 200 nm or more were 0.1% or less in area ratio to the whole islands, and islands having a diameter of 100 nm or more were 0.1% in area ratio. % Or less. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. Further, the yarn physical properties were excellent as shown in Table 2.
[0116]
After circular knitting of these polymer alloy fibers in the same manner as in Example 3, 99% or more of the copolymerized PET was removed by alkali treatment to obtain a circular knit consisting of N6 nanoporous fibers.
[0117]
When the cross section of the fiber of this N6 nanoporous fiber was observed by TEM, the density spots due to metal staining became finer than the original polymer alloy fiber, and the pore size became finer than the original island polymer by removing the island polymer. However, there were no large pores of 50 nm or more. From TEM observation, these pores were determined to be independent pores. In addition, the circular knit made of the N6 nanoporous fiber was dyed and evaluated for color development. The color development was excellent. The N6 nanoporous fiber had excellent physical properties as shown in Table 1.
[0118]
Comparative Example 1
Melt spinning was carried out in the same manner as in Example 3 using the device shown in FIG. The discharge of the polymer during spinning was not stable, and the spinnability was poor, and the yarn was frequently broken during spinning, and the yarn could not be stably wound. However, using a slightly obtained undrawn yarn, drawing and heat treatment were performed in the same manner as in Example 3 to obtain a polymer alloy fiber. Observation of the cross section of the obtained polymer alloy fiber by TEM revealed that the blend unevenness was large, coarse aggregated polymer particles were scattered, and the area ratio of the island having a diameter of 200 nm or more to the whole island was 10%. Using this, N6 porous fiber was obtained in the same manner as in Example 3. However, since the area ratio of the coarse pores having a diameter of 200 nm or more was as large as 2.0%, the scattered light was much whitish, and the coloring property was poor. Met.
[0119]
Comparative Example 2
After simply chip-blending 50% by weight of N6 used in Example 4, 2.5% by mole of 5-sodium sulfoisophthalic acid, and 50% by weight of polyethylene terephthalate copolymerized with 3.5% by mole of bisphenol A ethylene oxide adduct. The mixture was melted at 290 ° C., discharged from a round hole die having a hole diameter of 0.6 mm, and melt-spun at a spinning speed of 1200 m / min using the apparatus shown in FIG. However, the ejection of the polymer during spinning was not stable, and the spinnability was poor, and the yarn was frequently broken during spinning, and the yarn could not be stably wound. Using a slightly obtained undrawn yarn, it was drawn at a draw ratio of 2.7 times using a hot plate at 120 ° C. Thus, a polymer alloy fiber of 85 dtex and 24 filaments was obtained. Observation of the cross section thereof with a TEM revealed that the blend unevenness was large, coarse aggregated polymer particles were scattered, and the area ratio of the island having a diameter of 200 nm or more to the entire island was 10%.
[0120]
Then, 99% or more of the copolymerized PET was dissolved and removed therefrom by alkali treatment. At this time, the fiber diameter hardly changed. The color development was evaluated. As a result, the area ratio of the coarse pores having a diameter of 200 nm or more was as large as 5.0%, so that the scattered light was much whitish and the color development was poor.
[0121]
Comparative Example 3
70% by weight of N6 used in Example 4, 4.5% by mole of 5-sodium sulfoisophthalic acid having an intrinsic viscosity of 0.60, 8.5% by weight of polyethylene glycol having a molecular weight of 4000, and 30% by weight of polyethylene terephthalate copolymerized with 8.5% by weight. Was melted at 280 ° C., discharged from a round hole die having a hole diameter of 0.6 mm, and melt-spun at a spinning speed of 1000 m / min using the apparatus shown in FIG. However, the ejection of the polymer during spinning was not stable, and the spinnability was poor, and the yarn was frequently broken during spinning, and the yarn could not be stably wound. Using the slightly drawn undrawn yarn, drawing and heat treatment were performed at a draw ratio of 3.35 times, a temperature of the first hot roller 16 of 90 ° C., and a temperature of the second hot roller 17 of 130 ° C. Thus, a polymer alloy fiber of 85 dtex and 24 filaments was obtained. Observation of the cross section thereof with a TEM revealed that the blend unevenness was large, coarse aggregated polymer particles were scattered, and the area ratio of the island having a diameter of 200 nm or more to the whole island was 8%.
[0122]
Then, by an alkali treatment, 90% or more of the copolymerized PET was dissolved and removed therefrom. At this time, the fiber diameter hardly changed. The color development was evaluated, and it was found that the area ratio of the coarse pores having a diameter of 200 nm or more was as large as 2.4%.
[0123]
Comparative Example 4
77% by weight of N6 used in Example 4, 20% by weight of homo PET, and 3% by weight of a block polyether polyamide (45% by weight of a polyethylene glycol portion + 55% by weight of a poly-ε-caprolactam portion) as a compatibilizer. Melt spinning was performed in the same manner as in Example 1 by simply chip blending and using the apparatus shown in FIG. However, the ejection of the polymer during spinning was not stable, and the spinnability was poor, and the yarn was frequently broken during spinning, and the yarn could not be stably wound. Using a slightly obtained undrawn yarn, drawing and heat treatment were carried out in the same manner as in Example 1. Thus, a polymer alloy fiber of 77 dtex and 24 filaments was obtained. Observation of the cross section thereof with a TEM revealed that the blend unevenness was large, coarse aggregated polymer particles were scattered, and the area ratio of the island having a diameter of 200 nm or more to the entire island was 14%.
[0124]
Then, 99% or more of PET was dissolved and removed by alkali treatment. At this time, unlike Example 3, the fiber diameter hardly changed. The color development was evaluated. As a result, the area ratio of the coarse pores having a diameter of 200 nm or more was as large as 4.6%. Therefore, the scattered light was much whitish and the color development was poor.
[0125]
Comparative Example 5
Melt spinning was carried out in the same manner as in Comparative Example 3, except that the N6 / copolymerized PET blend ratio was 25% by weight / 75% by weight. However, the ejection of the polymer during spinning was not stable, and the spinnability was poor, and the yarn was frequently broken during spinning, and the yarn could not be stably wound. Using a slightly obtained undrawn yarn, it was drawn at a draw ratio of 2.7 times using a hot plate at 120 ° C. Thus, a polymer alloy fiber of 85 dtex and 24 filaments was obtained. Observation of the cross section by a TEM showed that unlike Comparative Example 1, N6, which was hardly soluble in alkali, was an island, and copolymer PET, which was easily soluble in alkali, was sea. In addition, the blend unevenness was large, coarse aggregated polymer particles were scattered, and the area ratio of the island having a diameter of 200 nm or more to the entire island was 10%.
[0126]
This was subjected to an alkali treatment in the same manner as in Example 1 to remove PET from the sea copolymer. As a result, a fiber in which N6 ultrafine fibers were strongly bonded was obtained. However, it was difficult to measure the strength of this fiber, and it was difficult to handle it as a practical fiber.
[0127]
Next, the polymer alloy fiber was treated with formic acid to dissolve and remove island N6. At the same time, however, the copolymerized PET was extremely embrittled, and it was difficult to handle as a practical fiber because it was easily broken. Thus, this polymer alloy fiber could not substantially obtain a porous fiber and could not achieve the object of the present invention.
[0128]
Reference Example 1
A copolymerized PET obtained by copolymerizing PET with 10 mol% of ethylene naphthalate with respect to all acid components (intrinsic viscosity: 0.60) and polyetherimide (“Ultem” -1000 manufactured by General Electric Co., Ltd.) is 70. The mixture was kneaded at 320 ° C. using a 30 mmφ biaxial extrusion kneader so as to obtain a weight%. The polymer alloy chip obtained here was sufficiently dried, and then melt-spun at a spinneret number of 6 holes, a single hole ejection amount of 0.6 g / min, a spinning temperature of 315 ° C., and a spinning speed of 500 m / min. The spinning temperature was too high compared to the melting point of the copolymer PET, which was a sea polymer, and the spinning became unstable, and the spinning was 12 times and the spinnability was poor. Using a slightly obtained undrawn yarn, drawing was performed at a preheating roller temperature of 90 ° C., a hot plate temperature of 120 ° C., and a draw ratio of 3.0 times, but yarn breakage occurred frequently. The strength of the drawn yarn obtained here was as low as 1.3 cN / dtex. This is presumably because the kneading temperature and the spinning temperature were too high for the copolymerized PET, which is a major component, to cause polymer degradation due to thermal decomposition. Also, the U% of this was extremely bad at 16%.
[0129]
Plain weave was prepared using this copolymerized PET alloy fiber for warp and weft. However, thread breakage and fluff frequently occurred, extremely poor process passability, and only poor quality woven fabric was obtained. The woven fabric was treated with a 6% by weight aqueous solution of NaOH at 90 ° C. for 2 hours to obtain spongy fibers. However, this had an extremely low strength of 0.3 cN / dtex. This is considered to be due to the fact that the copolymerized PET was originally thermally degraded and, furthermore, the copolymerized PET was disintegrated into tatters due to the treatment with a high concentration of alkali for a long time.
[0130]
As described above, if kneading and spinning conditions suitable for the polymer are not set, a high-strength, small-yarn yarn cannot be obtained, and the yarn-making properties also deteriorate. In addition, a small difference in solubility between the easily soluble polymer and the poorly soluble polymer also causes a reduction in strength. As described above, practically usable fibers can be obtained only by optimizing the kneading, spinning and dissolving conditions for each polymer.
[0131]
[Table 1]

[0132]
[Table 2]

[0133]
Example 15
Melting point 255 ° C., intrinsic viscosity 0.63, melt viscosity 830 poise (280 ° C., 2432 sec. ^-1 Melt kneading was carried out at 275 ° C. using a twin-screw extruder at 275 ° C. with 80% by weight of homo PET and 20% by weight of the hot water-soluble polymer used in Example 9. Melt spinning was performed in the same manner as in Example 3 except that the temperature of the melting part 2 was 280 ° C., the spinning temperature was 280 ° C., and the single hole discharge amount and the number of holes were changed. The number of yarn breaks during continuous spinning was zero. Then, stretching and heat treatment were performed in the same manner as in Example 3 except that the first hot roller temperature 16 was set to 90 ° C., and 90 dtex, 36 fragmentation, strength 3.3 cN / dtex, elongation 40%, U% 1.5%, heat A polymer alloy fiber having a shrinkage of 7% was obtained. As a result of observing the fiber cross section of the obtained polymer alloy fiber with a TEM (FIG. 21), the area ratio of the island having a diameter of 200 nm or more to the whole island not including coarse aggregated polymer particles was 0.1% or less, and the diameter was 0.1% or less. The area ratio of 100 nm or more was also 0.1% or less. Here, the dark part is PET and the thin part is hot water-soluble polymer. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. In addition, the yarn properties were excellent as shown in Table 4.
[0134]
After circular knitting of this polymer alloy fiber in the same manner as in Example 9, it was treated with hot water at 100 ° C. for 2 hours to remove 99% or more of the hot water-soluble polymer, thereby obtaining a circular knit made of PET nanoporous fiber.
[0135]
As a result of observing the fiber cross section of this PET nanoporous fiber by TEM (FIG. 22), the average diameter of the pores was 20 nm, and there were no large pores having a diameter of 50 nm or more. Here, the dark part was PET, the thin part was pores, and the pores were independent pores. Table 3 shows the physical properties of the nanoporous fiber.
[0136]
In addition, the circular knit made of the PET nanoporous fiber was dyed and evaluated for color development. The color development was excellent.
[0137]
Example 16
8 wt% of PEG1000 and 7 mol% of isophthalic acid were copolymerized with homo-PET (melting point: 235 ° C., intrinsic viscosity: 0.65, melt viscosity: 920 poise (280 ° C., 2432 sec.) ^-1 )), And melt-kneading was performed at 255 ° C. in the same manner as in Example 15. This was subjected to melt spinning in the same manner as in Example 15 except that the temperature of the melted portion 2 was set to 255 ° C., the spinning temperature was set to 255 ° C., and the shape of the die hole was set to the Y section. The thread break was zero. Then, drawing and heat treatment were performed in the same manner as in Example 15 to obtain a polymer alloy fiber having a trilobal cross section. As a result of observing the fiber cross section of the obtained polymer alloy fiber with a TEM, the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles is 0.1% or less, and the area of the island is 100 nm or more. The ratio was also 0.1% or less. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. In addition, the yarn properties were excellent as shown in Table 4.
[0138]
After circular knitting of this polymer alloy fiber in the same manner as in Example 15, it was treated with hot water at 100 ° C. for 2 hours to remove 99% or more of the hot water-soluble polymer to obtain a circular knit made of PET nanoporous fiber.
[0139]
As a result of observing the cross section of the PET nanoporous fiber with a TEM, the average diameter of the pores was 20 nm, and there were no large pores having a diameter of 50 nm or more. TEM observation revealed that the pores were independent pores. Table 3 shows the physical properties of the nanoporous fiber.
[0140]
In addition, the circular knit made of the PET nanoporous fiber was dyed and evaluated for color development. The color development was excellent.
[0141]
Examples 17 and 18
The copolymerized PET was melted at a melting point of 220 ° C. and a melt viscosity of 1290 poise (280 ° C., 2432 sec. ^-1 ) Of polytrimethylene terephthalate (PTT) or a melting point of 220 ° C. and a melt viscosity of 550 poise (280 ° C., 2432 sec.) ^-1 As in Example 15, melt kneading, melt spinning, drawing and heat treatment were performed for polybutylene terephthalate (PBT). As a result of observing the fiber cross section of the obtained polymer alloy fiber with a TEM, the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles is 0.1% or less, and the area of the island is 100 nm or more. The ratio was also 0.1% or less. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. In addition, the yarn properties were excellent as shown in Table 4.
[0142]
This polymer alloy fiber was circular knitted in the same manner as in Example 15 and then treated with hot water at 100 ° C. for 2 hours to remove 99% or more of the hot water-soluble polymer to obtain a circular knit made of polyester nanoporous fiber.
[0143]
As a result of observing the fiber cross section of this polyester nanoporous fiber with a TEM, the average diameter of the pores was 20 nm, and there were no large pores having a diameter of 50 nm or more. TEM observation revealed that the pores were independent pores. Table 3 shows the physical properties of the nanoporous fiber.
[0144]
In addition, the circular knit made of the polyester nanoporous fiber was dyed and evaluated for color development. The color development was excellent.
[0145]
Example 19
PET was melted at 170 ° C. and melt viscosity was 1200 poise (280 ° C., 2432 sec.) ^-1 )), And kneading was carried out in the same manner as in Example 15 except that the melting temperature was 220 ° C. When the melt spinning was performed in the same manner as in Example 15 except that the temperature of the melted portion 2 was set to 220 ° C. and the spinning temperature was set to 220 ° C., the spinnability was good and the yarn breakage during continuous spinning for 24 hours was zero. . Then, stretching and heat treatment were performed in the same manner as in Example 3, except that the first hot roller temperature 16 was set to 90 ° C. As a result of observing the fiber cross section of the obtained polymer alloy fiber with a TEM, the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles is 0.1% or less, and the area of the island is 100 nm or more. The ratio was also 0.1% or less. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. In addition, the yarn physical properties were excellent as shown in Table 4.
[0146]
After circular knitting of this polymer alloy fiber in the same manner as in Example 15, it was treated with hot water at 100 ° C. for 2 hours to remove 99% or more of the hot water-soluble polymer, thereby obtaining a circular knit made of PLA nanoporous fiber.
[0147]
As a result of observing the fiber cross section of this PLA nanoporous fiber with a TEM, the average diameter of the pores was 20 nm, and there were no large pores having a diameter of 50 nm or more. Table 3 shows the physical properties of the nanoporous fiber.
[0148]
In addition, the circular knit made of the PLA nanoporous fiber was dyed and evaluated for color development. The color development was excellent. In particular, PLA had a problem that the dye exhaustion rate was low. However, by making it nanoporous, the dye exhaustion rate was improved, and the coloring property was improved as compared with ordinary PLA fibers.
[0149]
Examples 20 and 21
Using PLA as polypropylene (PP) or polymethyl methacrylate (PMMA), melt kneading, melt spinning, drawing and heat treatment were performed in the same manner as in Example 17. As a result of observing the fiber cross section of the obtained polymer alloy fiber with a TEM, the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles is 0.1% or less, and the area of the island is 100 nm or more. The ratio was also 0.1% or less. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. In addition, the yarn properties were excellent as shown in Table 4.
[0150]
This polymer alloy fiber was circular knitted in the same manner as in Example 15 and then treated with hot water at 100 ° C. for 2 hours to remove 99% or more of the hot water-soluble polymer, thereby obtaining a circular knit made of PP or PMMA nanoporous fiber. Table 3 shows the physical properties of the nanoporous fiber.
[0151]
Example 22
Melt kneading was performed in the same manner as in Example 15 except that PET was polymethylpentene (PMP) and the melting temperature was 255 ° C. When the melt spinning was performed in the same manner as in Example 15 except that the temperature of the melted part 2 was set to 255 ° C. and the spinning temperature was set to 255 ° C., the spinnability was good and the yarn breakage during continuous spinning for 24 hours was zero. . Then, stretching and heat treatment were performed in the same manner as in Example 3, except that the first hot roller temperature 16 was set to 90 ° C. As a result of observing the fiber cross section of the obtained polymer alloy fiber with a TEM, the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles is 0.1% or less, and the area of the island is 100 nm or more. The ratio was 1.2%. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. In addition, the yarn properties were excellent as shown in Table 4.
[0152]
This polymer alloy fiber was circularly knitted in the same manner as in Example 15 and then treated with hot water at 100 ° C. for 2 hours to remove 99% or more of the hot water-soluble polymer, thereby obtaining a circular knit made of PMP nanoporous fiber.
[0153]
As a result of observing the cross section of the fiber of this PMP nanoporous fiber by TEM, the average diameter of the pores was 30 nm, and the area of large pores having a diameter of 50 nm or more was 0.3% of the whole pores. Table 3 shows the physical properties of the nanoporous fiber.
[0154]
Example 23
Melt kneading was performed at 305 ° C. in the same manner as in Example 15 except that PET was polyphenylene sulfide (PPS), the hot water-soluble polymer was N6 used in Example 2, and the blend ratio of PPS was 90% by weight. When the melt spinning was performed in the same manner as in Example 15 except that the temperature of the melting part 2 was 305 ° C., the spinning temperature was 305 ° C., and the discharge amount per hole and the number of holes were changed, continuous spinning for 24 hours was performed. The number of thread breaks during this was two. Then, drawing and heat treatment were performed in the same manner as in Example 3 except that the first hot roller temperature 16 was set to 90 ° C., and a 150 dtex, 48 filament polymer alloy fiber was obtained. As a result of observing the fiber cross section of the obtained polymer alloy fiber by TEM, it was found that the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles was 1.5%. Further, it was found from the fiber longitudinal section TEM observation that the island had a streak structure. In addition, the yarn properties were excellent as shown in Table 4.
[0155]
This polymer alloy fiber was circular knitted in the same manner as in Example 15 and then treated with formic acid for 2 hours to remove 99% or more of N6 to obtain a circular knit composed of PPS nanoporous fibers. Table 3 shows the physical properties of the nanoporous fiber.
[0156]
[Table 3]

[0157]
[Table 4]

[0158]
Example 24
"Lycra" (registered trademark), a polyurethane fiber yarn manufactured by Operontex, was covered using the N6 / copolymerized PET alloy false twisted yarn produced in Example 1 as a sheath yarn. Then, a knitted fabric for tights was produced using the covering yarn, and then an alkali treatment was performed in the same manner as in Example 1 to produce a knitted fabric for tights made of N6 nanoporous fiber. The basis weight of this knitted fabric for tights is 100 g / m. ² And the weight ratio of N6 nanofiber to polyurethane fiber yarn was 95% and 5%, respectively. This was subjected to silicone treatment and rubbing treatment. Then, the knitted fabric for tights was sewn to produce tights. The N6 nanoporous fiber was extracted from the tights and observed with a TEM. As a result, there were no coarse pores having a diameter of 50 nm or more, and the average diameter of the pores was 25 nm. The pores were independent pores. The yarn strength was 2.5 cN / dtex. The tights had good coloring properties, a high ΔMR of 5.6%, a delicate touch and a moist and fresh texture like human skin, and were extremely comfortable to wear. In addition, the use of polyurethane fibers not only provided a large stretch property, but also improved the form stability of tights during washing.
[0159]
Example 25
Melt spinning was performed in the same manner as in Example 1 except that the single hole discharge amount and the number of holes were changed, and the spinning speed was set at 3800 m / min, to obtain a 400 dtex, highly oriented undrawn yarn composed of 96 filaments of N6 / copolymerized PET polymer alloy fiber. Obtained. This polymer alloy highly oriented undrawn yarn had a strength of 2.5 cN / dtex, an elongation of 100%, and a U% of 1.2%. As a result of observing the cross section of the fiber by TEM, it was found that the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles was 0.1% or less, and the average diameter of the island was 39 nm. Then, this was subjected to draw false twisting in the same manner as in Example 1 using the apparatus shown in FIG. 27 to obtain a 333 dtex, 96 filament false twisted yarn. The obtained false twisted yarn had a strength of 3.0 cN / dtex and an elongation of 30%. As a result of observing the cross section of the fiber of the obtained polymer alloy crimped yarn with a TEM, the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles was 0.1% or less, and the diameter was 100 nm or more. Was also 0.1% or less. The average diameter of the island was 27 nm.
[0160]
The false twisted yarn was subjected to a sweet twist of 300 turns / m, and an S-twisted / Z-twisted twin yarn was used as a warp and a weft to produce a 2/2 twill fabric. Then, the obtained twill fabric is subjected to an alkali treatment in the same manner as in Example 1, and the basis weight of N6 nanoporous fiber is 150 g / m. ² Was obtained. The N6 nanoporous fiber was extracted from the curtain fabric and observed with a TEM. As a result, there were no coarse pores having a diameter of 50 nm or more, and the average diameter of the pores was 25 nm. The pores were independent pores. The yarn strength was 2.5 cN / dtex.
[0161]
In addition, this curtain had good color developability, and showed a sufficient moisture absorbency (ΔMR) of 5.5%. Then, when a curtain was produced using this cloth and hung between six tatami mats, dew condensation was suppressed by high moisture absorption, and furthermore, by eliminating deodorant gas, a fresh indoor environment could be achieved. As described above, the nanoporous fiber of the present invention was suitable for an environment-responsive interior product that could prepare an unprecedented indoor environment. In addition, this curtain was washed and dehydrated by placing it in a washing net with a home washing machine, but it did not lose its shape. Unlike rayon curtains, it had good dimensional stability even though it had high moisture absorption and high water absorption. Showed sex.
[0162]
Example 26
Melt spinning was performed in the same manner as in Example 3 except that the single hole discharge amount and the number of holes were changed, and the discharge holes were changed to Y type. The spun yarn is drawn at 900 m / min, and then subjected to two-stage drawing under the condition that the first-stage drawing ratio is 1.3 times and the total ratio is 3.5 times, and further crimping is performed using a jet nozzle. Then, a bulky processed yarn of 500 dtex and 90 filaments was wound up. The bulky yarn had a strength of 5.0 cN / dtex and an elongation of 25%. As a result of observing the cross section of the fiber of the obtained polymer alloy crimped yarn with a TEM, the area ratio of the island having a diameter of 200 nm or more to the entire island without containing coarse aggregated polymer particles was 0.1% or less, and the diameter was 100 nm or more. Was also 0.1% or less. The average diameter of the island was 30 nm.
[0163]
Two of the obtained bulky yarns are drawn and aligned, ply-twisted (200 T / m), twisted by two-ply twisting (200 T / m), and twist-stopped at 170 ° C. dry heat. , And tufted by a known method as a cut pile carpet. At this time, with a normal level cut, 1/10 gauge, the basis weight is 1500 g / m ² I adjusted the stitch so that it became tufted. After that, backing was performed. At the time of tufting, a woven base fabric using a blend yarn of acrylic fiber and polyester fiber was used as the base fabric. Further, only the cut pile portion was subjected to alkali treatment, and a structure in which the cut pile portion was an N6 nanoporous fiber was developed. When this was observed with a TEM, there were no coarse pores having a diameter of 50 nm or more, and the average diameter of the pores was 30 nm. The pores were independent pores. Further, when the cut pile was pulled out and the strength was measured, it was 2.0 cN / dtex. The cut pile portion had good color developability, ΔMR of 5.3%, sufficient moisture absorption, a fresh indoor environment, and dew condensation could be suppressed.
[0164]
Example 27
The spinning was performed in the same manner as in Example 3 except that the spinneret and the single hole discharge amount were changed. After the yarn was taken up by the first take-up roller 8, the yarn was combined and received by a bunker. Then, the yarn received by the bunker was further combined into a 150,000 dtex tow. This was stretched 3.2 times in a 90 ° C. water bath. Then, after passing through a crimper, it was refueled and cut. The obtained cut fiber had a single fiber fineness of 7 dtex, a number of crimps of 10/25 mm, and a fiber length of 51 mm. For the number of crimps, 30 mm of cut fiber single yarn was sampled, and the number of crimps was counted. The cut fiber had a strength of 3.3 cN / dtex and an elongation of 40%. As a result of observing the cross section of the fiber with a TEM, the area ratio of the islands having a diameter of 200 nm or more to the whole islands without containing coarse aggregated polymer particles was 0.1% or less, and the area ratio of the islands having a diameter of 100 nm or more was 0%. 0.7%. The average diameter of the island was 33 nm.
[0165]
After the cut fiber was defibrated with a card, the web was formed with a cross wrap weber. Next, needle punch (1500 times / cm ² ), 180 g / m ² Fiber entangled nonwoven fabric. This nonwoven fabric was subjected to the alkali treatment in the same manner as in Example 3, to obtain an N6 nanoporous fiber nonwoven fabric. When nanoporous fibers were sampled from this nonwoven fabric and observed by TEM, there were no coarse pores having a diameter of 50 nm or more, and the average diameter of the pores was 30 nm. The pores were independent pores. When the cut fiber was treated with alkali and made into a nanofiber, the strength was measured and found to be 2 cN / dtex. This nonwoven fabric also had a good coloring property and exhibited a sufficient hygroscopicity of ΔMR = 5.8%.
[0166]
Example 28
A cut fiber made of the polymer alloy prepared in Example 27 was spun to obtain a polymer alloy spun yarn. This is used for warp and weft, and has a basis weight of 150 g / m. ² I got a plain weave. Then, alkali treatment was performed in the same manner as in Example 1 to obtain an N6 nanoporous fiber cloth. When nanoporous fibers were sampled from this cloth and observed by TEM, there were no coarse pores having a diameter of 50 nm or more, and the average diameter of the pores was 30 nm. The pores were independent pores. Further, when the nanoporous fiber spun yarn was pulled out from this fabric and its strength was specified, it was 2.0 cN / dtex. This fabric also had good color developability, exhibited a sufficient hygroscopicity of ΔMR = 5.8%, and also had good color developability.
[0167]
Example 29
Spinning was carried out in the same manner as in Example 20, and the yarn was taken out by air soccer, opened, collected on a net, and then covered with a calender roll to give a basis weight of 35 g / m made of a polymer alloy fiber. ² Was obtained. The single yarn fineness of the fiber taken by air soccer was 2 dtex, and the spinning speed determined from the fineness was equivalent to 4500 m / min. As a result of extracting a polymer alloy fiber from this nonwoven fabric and observing the cross section of the fiber with a TEM, the area ratio of an island having a diameter of 200 nm or more to an entire island without containing coarse aggregated polymer particles is 0.1% or less, and an island having a diameter of 100 nm or less. Was also 0.1% or less. The average diameter of the island was 31 nm.
[0168]
This nonwoven fabric was subjected to hot water treatment in the same manner as in Example 14, to obtain a PP nanoporous fiber nonwoven fabric. This was excellent in water absorption. When nanoporous fibers were sampled from this nonwoven fabric and observed by TEM, there were no coarse pores having a diameter of 50 nm or more, and the average diameter of the pores was 30 nm. As described above, the nanoporous fiber of the present invention was optimal for obtaining an unprecedented high-performance nonwoven fabric.
[0169]
Example 30
The polymer alloy fiber produced in Example 14 and ordinary N6 fiber of 70 dtex and 96 filaments were air-blended using an interlace nozzle. This is used for warp and weft, and has a basis weight of 150 g / m. ² Was prepared and subjected to an alkali treatment in the same manner as in Example 3 to obtain a fabric comprising N6 nanoporous fibers and normal N6. When this N6 nanoporous fiber was observed by TEM, there were no coarse pores having a diameter of 50 nm or more, the average diameter of the pores was 20 nm, and the yarn strength was 3.3 cN / dtex. The pores were independent pores. This fabric had good color developability and also had a ΔMR of 4%, indicating a sufficient hygroscopicity. This was also an excellent texture with a soft and delicate touch.
[0170]
Example 31
Melt spinning was performed in the same manner as in Example 3 except that the discharge amount and the number of holes were changed, and a high orientation consisting of a polymer alloy having 90 dtex, 68 filaments, a strength of 2.7 cN / dtex, an elongation of 100%, and U% of 1.3% was used. The undrawn yarn was wound up. This was combined with a separately prepared 70 dtex, 34 filament ordinary N6 drawn yarn (strength 6 cN / dtex, elongation 45%). At this time, the draw ratio was 1.02 times, and the heater temperature was 165 ° C. A circular knit was produced using the obtained composite false-twisted CR37% yarn in the same manner as in Example 1 and subjected to an alkali treatment. The N6 nanoporous fiber was extracted from the obtained circular knitting and observed by TEM. As a result, there was no coarse pore having a diameter of 50 nm or more, the average diameter of the pore was 15 nm, and the yarn strength was 2.5 cN / dtex. The pores were independent pores. This fabric had good color developability and also had a ΔMR of 4.5%, indicating a sufficient hygroscopicity. This was also an excellent texture with a soft and delicate touch.
[0171]
Example 32
The polymer alloy fiber obtained in Example 4 was used for a 72 dtex, 27 filament viscose rayon weft as a warp, and the basis weight was 150 g / m. ² Thus, a 2/2 twill fabric was produced. This was subjected to an alkali treatment in the same manner as in Example 1. The N6 nanoporous fiber was extracted from the obtained fabric and observed with a TEM. As a result, there was no coarse pore having a diameter of 50 nm or more, the average diameter of the pore was 15 nm, and the yarn strength was 2.5 cN / dtex. The pores were independent pores. This fabric had good color developability and also showed a ΔMR of 7%, indicating a sufficient hygroscopicity. This was also an excellent texture with a soft and delicate touch. As described above, by mixing the nanoporous fiber of the present invention with other fibers, the texture and the hygroscopicity can be further improved, and the nanoporous fiber is most suitable for high-grade clothing fabric.
[0172]
Example 33
A cloth made of the PET nanoporous fiber obtained in Example 15 was exhausted with a moisture absorbent, trade name “SR1000” (trade name, manufactured by Takamatsu Yushi Co., Ltd.) (10% aqueous dispersion). At this time, the processing conditions were as follows: the moisture absorbing agent was 20% owf as solids, the bath ratio was 1:20, the processing temperature was 130 ° C., and the processing time was 1 hour. The exhaustion rate of this moisture absorbent into ordinary polyester fibers is almost 0%, but the exhaustion rate into this PET nanoporous fiber is 12% or more, and ΔMR = 4% or more, which is excellent moisture absorption equivalent to cotton. A PET fabric having properties was obtained. As described above, the nanoporous fiber of the present invention has a structure in which a functional substance is easily taken in and encapsulated, so that the exhaustion rate of the functional substance can be improved, and the nanoporous fiber is optimal as a functional processing yarn. is there.
[0173]
Comparative Example 6
A normal PET fabric was subjected to moisture absorption in the same manner as in Example 33, but the exhaustion rate of the moisture absorbent was almost 0%, and no moisture absorption was exhibited.
[0174]
Example 34
Triphenylphosphoric acid as a flame retardant ("Leophos TPP", Ajinomoto Fine Techno Co., Ltd.) as a flame retardant was added to a fabric made of the PET nanoporous fiber prepared in Example 15 at 20% owf, a bath ratio of 1:40, a treatment temperature of 130 ° C., and a treatment. Exhausted in 1 hour. Then, this was washed with water and soaped with an aqueous sodium carbonate solution (80 ° C.). Furthermore, home washing was performed 10 times. At this time, the adhered amount was 7% by weight, and a good self-extinguishing property was shown in the evaluation of combustion. As described above, the nanoporous fiber of the present invention easily incorporates the functional substance and as if it were encapsulated. Due to the structure, washing durability can be improved, and it is optimal as a raw yarn for functional processing.
[0175]
Comparative Example 7
A normal PET fabric was subjected to flame retarding in the same manner as in Example 34. The amount of adhesion after washing 10 times was 1% by weight, and when evaluated for combustion, no self-extinguishing property was exhibited.
[0176]
Example 35
The squalane, which is a natural oil component extracted from shark liver and has a skin care effect by moisturizing, was exhausted to the cloth made of the PET nanoporous fiber obtained in Example 15. The processing conditions at this time are a mixture of 60% squalane and 40% emulsifying dispersant, dispersed in water at a concentration of 7.5 g / liter, a bath ratio of 1:40, a temperature of 130 ° C., and a processing time of 60 minutes. After the treatment, washing was performed at 80 ° C. for 2 hours, and the amount of squalane attached at this time was 21% by weight based on the cloth. Thereafter, the amount of squalane adhered after home washing 20 times was 12% by weight with respect to the fabric, indicating sufficient washing durability.
[0177]
A sock was prepared using a circular knit made of this squalane-processed PET nanoporous fiber, and a 10-week wearing test was performed on 10 subjects with severely dried heels. . This is probably because squalane trapped or encapsulated in the pores was gradually extracted by the subject's sweat and came into contact with the skin.
[0178]
Comparative Example 8
When squalane was exhausted to a normal PET cloth in the same manner as in Example 36, the adhesion amount after washing was 21% by weight based on the cloth, but the adhesion amount after 10 home washings was 0%. %, And there was no washing durability at all.
[0179]
Example 36
The N6 nanoporous fiber fabric prepared in Example 3 was immersed in ion-exchanged water, and then 1,2-bis (trimethoxysilyl) ethane was added and stirred for 3 hours. After standing at room temperature for 14 hours, the mixture was further stirred for 13 hours. After standing at room temperature for 14 hours, the mixture was further stirred for 7 hours to polymerize silica. Thereafter, the circular knitted fabric was washed with ion-exchanged water and air-dried. By this operation, a fabric-shaped N6 / silica composite was obtained using the pores of the N6 nanofiber as a template. This was an excellent material having both sufficient rigidity and flexibility. It was also a hybrid material with excellent flame retardancy. The ratio of silica in the composite was 30% by weight.
[0180]
As described above, the nanoporous fiber of the present invention can be easily converted into a hybrid material by exhausting a polymerizable or crosslinkable monomer or oligomer and then polymerizing or crosslinking it. Therefore, it is most suitable as a precursor for obtaining advanced materials such as an organic material having the function of an inorganic material (flame retardant, catalyst, etc.) and a flexible inorganic material.
[0181]
Example 37
Tights made of the N6 nanoporous fiber prepared in Example 24 were impregnated with "New Polykine Solution" manufactured by Taiho Pharmaceutical Co., Ltd., and dried. In this way, tights from which the athlete's foot drug can be eluted by sweat were obtained. The tights were worn by athlete's foot patients and were replaced with new ones every day. When this was continued for one month, the symptom was improved due to the sustained release of the athlete's foot drug.
[0182]
As described above, the nanoporous fiber of the present invention is suitable as a medical product because it has a sustained release ability of the active ingredient.
[0183]
Example 38
The deodorizing test of the N6 nanoporous fiber cloth obtained in Example 1 was performed by the following method. That is, after 3.0 g of the sample cloth was fixed in a 500 ml polyethylene container, a malodorous substance was introduced into the container. After sealing, the container was kept at 50 ° C. for 1 minute to sufficiently vaporize the offensive odor substance. Then, after standing at 30 ° C. for a predetermined time, the air in the container was sampled, and the concentration of the offensive odor substance was measured with a gas detection tube manufactured by Gastech Co. When ammonia was used as an offensive odor substance, the odor could be deodorized from an initial concentration of 200 ppm to 20 ppm in 10 minutes. When hydrogen sulfide gas was used, the odor could be deodorized from an initial concentration of 45 ppm to 2 ppm in 10 minutes.
[0184]
Comparative Example 9
When a deodorizing test was performed in the same manner as in Example 39 using a normal N6 cloth, ammonia was used in an initial concentration of 130 ppm for 10 minutes from 200 ppm, and when hydrogen sulfide gas was used, an initial concentration of 45 ppm was used for 10 minutes. Deodorization was possible only up to 10 ppm.
[0185]
Example 39
The N6 nanoporous fiber cloth obtained in Example 1 was immersed in a 3% aqueous solution of diethylenetriamine at 50 ° C. for 1 minute to support diethylenetriamine on the N6 nanoporous fiber. When the acetaldehyde removal ability was evaluated, the concentration was reduced from 30 ppm to 1 ppm in 10 minutes, showing excellent removal ability.
[0186]
As described above, the nanoporous fiber of the present invention has a capability of supporting an adsorbent, and thus is suitable as an industrial material product such as a chemical filter or an air filter.
[0187]
Example 40
After melting the polymer alloy prepared in Example 1 as a core component and N6 used in Example 1 as a sheath component at 270 ° C., core-sheath composite spinning is performed at a spinning temperature of 275 ° C., and drawing at 3800 m / min. An undrawn yarn was obtained. This was subjected to stretch false twisting in the same manner as in Example 1. Here, the composite ratio of the polymer alloy was 80% by weight. The obtained core-sheath composite crimped yarn had 150 dtex, 76 filaments, strength of 4.0 cN / dtex, elongation of 27%, U% of 1.0%, heat shrinkage of 10% and CR of 45%. In the polymer alloy as the core component, the island copolymerized PET was finely dispersed with an average diameter of about 26 nm, and coarse islands having a diameter of 100 nm or more accounted for 0.1% or less of the area ratio of the entire islands. Using the core-sheath composite crimped yarn obtained here, circular knitting and alkali treatment were performed in the same manner as in Example 1 to obtain a circular knit made of N6 nanoporous fiber. From this, the nanoporous fiber was taken out and observed by TEM. As a result, there was no coarse pore having a diameter of 50 nm or more, and the average diameter of the pore was 20 nm. The area of the nanoporous portion was 77% with respect to the fiber cross section. Moreover, the yarn strength of the nanoporous fiber was 3.3 cN / dtex, which was higher than that of Example 1 and excellent in abrasion resistance. The pores were independent pores. This fabric had a more vivid color development than that of Example 1, and also had a ΔMR of 4.8%, indicating a sufficient hygroscopicity.
[0188]
Example 41
The core component and the sheath component were exchanged, and the composite ratio of the polymer alloy was changed to 50% by weight, and the core-sheath composite spinning and drawing false twisting were performed in the same manner as in Example 41, 150 dtex, 76 filaments, strength 4.1 cN / dtex, elongation 27. %, U% 1.0%, heat shrinkage 10%, and CR-45% core-sheath composite crimped yarn. In the polymer alloy as the sheath component, the island-copolymerized PET was finely dispersed with an average diameter of about 26 nm, and coarse islands having a diameter of 100 nm or more accounted for 0.1% or less of the total area of the islands. Using the obtained core-sheath composite crimped yarn, circular knitting and alkali treatment were performed in the same manner as in Example 41 to obtain a circular knit made of N6 nanoporous fiber. From this, the nanoporous fiber was taken out and observed by TEM. As a result, there was no coarse pore having a diameter of 50 nm or more, and the average diameter of the pore was 20 nm. The area of the nanoporous portion was 45% with respect to the fiber cross section. The nanoporous fiber had a yarn strength of 3.5 cN / dtex, which was higher than that of Example 1. The pores were independent pores. This fabric had good color developability and also had a ΔMR of 4%, indicating a sufficient hygroscopicity.
[0189]
Example 42
Assuming that the N6 alone side was the high viscosity N6 used in Example 5 and that the polymer alloy was prepared in Example 1, a composite spinning was performed in the same manner as in Example 41 as a side-by-side composite at a composite ratio of 50% by weight / 50% by weight. went. The obtained undrawn yarn is drawn and heat-treated at a draw ratio of 1.2 times in the same manner as in Example 3 to obtain 110 dtex, 34 filaments, strength 4.1 cN / dtex, elongation 27%, U% 1.2%, and heat shrinkage. A side-by-side crimped yarn having a rate of 10% and a crimp count of 20 pieces / 25 mm was obtained. In the polymer alloy which is a component outside the crimp, the island-copolymer PET was finely dispersed with an average diameter of about 26 nm, and coarse islands having a diameter of 100 nm or more were 0.1% or less in area ratio with respect to the entire island. Using the side-by-side crimped yarn obtained here, circular knitting and alkali treatment were performed in the same manner as in the example to obtain a circular knit made of N6 nanoporous fiber. From this, the nanoporous fiber was taken out and observed by TEM. As a result, there was no coarse pore having a diameter of 50 nm or more, and the average diameter of the pore was 20 nm. The area of the nanoporous portion was 44% with respect to the fiber cross section. Further, the nanoporous fiber had sufficient bulkiness, and had a high yarn strength of 3.5 cN / dtex. The pores were independent pores. This fabric had good color developability and also had a ΔMR of 4%, indicating a sufficient hygroscopicity. In addition, when the fabric absorbed water, the bulkiness was further improved.
[0190]
Example 43
N6 alone was used as the low-viscosity N6 used in Example 1 and the polymer alloy side was prepared in Example 5 and subjected to composite spinning, drawing and heat treatment in the same manner as in Example 43, 110 dtex, 34 filaments, strength 4. A side-by-side crimped yarn having 0 cN / dtex, an elongation of 25%, U% of 1.2%, a heat shrinkage of 10%, and a number of crimps of 18/25 mm was obtained. In the polymer alloy which is a component inside the crimp, the island-copolymer PET was finely dispersed with an average diameter of 18 nm, and coarse islands having a diameter of 100 nm or more were 0.1% or less in area ratio to the whole islands. Using the side-by-side crimped yarn obtained here, circular knitting and alkali treatment were performed in the same manner as in Example 41 to obtain a circular knit made of N6 nanoporous fiber. From this, the nanoporous fiber was taken out and observed by TEM. As a result, there was no coarse pore having a diameter of 50 nm or more, and the average diameter of the pore was 20 nm. The area of the nanoporous portion was 45% with respect to the fiber cross section. Further, the nanoporous fiber had sufficient bulkiness, and the yarn strength was as high as 3.4 cN / dtex. The pores were independent pores. This fabric had good color developability and also had a ΔMR of 4%, indicating a sufficient hygroscopicity. In addition, when the fabric absorbed water, the crimp was expanded and the stitches were expanded, and the air permeability was improved.
[0191]
Example 44
The circular knit made of the polymer alloy fiber obtained in Example 3 was treated with a 2% aqueous sodium hydroxide solution (95 ° C., bath ratio 1:40) for 20 minutes to remove 50% of the copolymerized PET in the polymer alloy fiber. It decomposed and eluted (the weight loss rate as a fiber was 10%). The elution proceeded in a ring shape from the fiber surface layer, and the nanoporous portion was 50% of the fiber cross section. As a result of TEM observation of this portion, the pores were independent pores, the average diameter of which was 20 nm, and there were no coarse pores having a diameter of 50 nm or more.
[0192]
This circular knitting was ΔMR = 4.0%. Showed good adhesion. In addition, the water retention was 60%, which was sufficient. This also showed reversible water swelling, but the swelling ratio was as low as 4%, and the dimensional stability was improved as compared with Example 3.
[0193]
Example 45
The polymer alloy crimped yarn prepared in Example 1 was used for warp and weft, and 170 g / m ² Was produced. This was subjected to an alkali treatment in the same manner as in Example 1 to produce a plain weave made of N6 nanoporous fibers. From this, the nanoporous fiber was extracted, and the form and physical properties were measured. As a result, the same values as in Example 1 were obtained. When buffing treatment was applied thereto, the surface layer of the nanoporous fiber was fibrillated, and a large number of fibrils having a fiber diameter of about 0.01 to 1 μm were formed, covering the woven fabric surface. As a result, not only a soft touch with a sense of span was obtained, but also water repellency was exhibited even with no coating, and the fabric was suitable as a sports cloth.
[0194]
Comparative Example 10
Using a normal N6 false twisted yarn (77 dtex, 34 filaments), a high-density plain weave was produced and buffed in the same manner as in Example 46, but the fibrillation was insufficient, and the fibrils did not cover the woven fabric surface. In addition, the number of pills (pills) increased, and not only the surface appearance became dirty, but also a soft touch with a span feeling could not be obtained. In addition, when the buffing treatment was performed tightly to promote fibrillation, the fabric was broken.
[0195]
Example 46
The polymer alloy crimped yarn prepared in Example 1 was used as the weft, and the warp was usually made of N6 fiber (44 dtex, 12 filaments) using 180 g / m2. ² 5 back satin was prepared. This was subjected to an alkali treatment in the same manner as in Example 1 to produce a back satin fabric composed of N6 nanoporous fibers. From this, the nanoporous fiber was extracted, and the form and physical properties were measured. As a result, the same values as in Example 1 were obtained. This was subjected to a buffing process. As a result, the surface layer of the nanoporous fiber was fibrillated, and a large number of fibrils having a fiber diameter of about 0.01 to 1 μm were formed, covering the woven fabric surface. Thereafter, a water punch treatment was further performed to further open the fibrils. This was suitable as a fabric for living material products such as wiping cloth.
[0196]
Example 47
When the nonwoven fabric made of the N6 nanoporous fiber obtained in Example 27 was subjected to a buffing treatment, a large number of fibrils having a fiber diameter of about 0.01 to 1 μm were also formed, covering the nonwoven fabric surface. This was a soft surface touch not found in conventional nylon nonwoven fabrics.
[0197]
Example 48
When the nonwoven fabric made of the PP nanoporous fiber obtained in Example 29 was subjected to buffing treatment, a large number of fibrils having a fiber diameter of about 0.01 to 1 μm were formed and covered the nonwoven fabric surface. Since the surface area was larger than that of the conventional PP spunbonded nonwoven fabric, the efficiency of trapping particles and the efficiency of electret processing were high, and this was suitable for filters.
[0198]
【The invention's effect】
The nanoporous fiber of the present invention, in which nanopores containing almost no large coarse pores are uniformly dispersed, can greatly improve the coloring property as compared with conventional porous fibers, and have a high addition utilizing the excellent moisture absorption and adsorption characteristics. You can get valuable textile products.
[Brief description of the drawings]
FIG. 1 is a TEM photograph showing a cross section of a nanoporous fiber of Example 1.
FIG. 2 is a TEM photograph showing a cross section of the polymer alloy fiber of Example 1.
FIG. 3 is a TEM photograph showing a cross section of a polymer alloy fiber of Example 3.
FIG. 4 is a TEM photograph showing a longitudinal section of a polymer alloy fiber of Example 3.
FIG. 5 is a TEM photograph showing a cross section of a nanoporous fiber of Example 3.
FIG. 6 is a TEM photograph showing a longitudinal section of a nanoporous fiber of Example 3.
FIG. 7 is a TEM photograph showing a cross section of the polymer alloy chip of Example 3.
FIG. 8 is a TEM photograph showing a cross section of the polymer alloy fiber of Example 6.
FIG. 9 is a TEM photograph showing a cross section of the nanoporous fiber of Example 6.
FIG. 10 is a TEM photograph showing a cross section of a polymer alloy fiber of Example 7.
FIG. 11 is a TEM photograph showing a cross section of a nanoporous fiber of Example 7.
FIG. 12 is a TEM photograph showing a cross section of a polymer alloy fiber of Example 8.
FIG. 13 is a TEM photograph showing a cross section of the nanoporous fiber of Example 8.
FIG. 14 is a TEM photograph showing a fiber cross section of the polymer alloy fiber of Example 11.
FIG. 15 is a TEM photograph showing a cross section of a polymer alloy fiber of Example 11.
FIG. 16 is a TEM photograph showing a longitudinal section of a polymer alloy fiber of Example 11.
FIG. 17 is a TEM photograph showing a cross section of the nanoporous fiber of Example 11.
FIG. 18 is a TEM photograph showing a longitudinal section of a nanoporous fiber of Example 11.
FIG. 19 is a TEM photograph showing a cross section of the polymer alloy fiber of Example 12.
FIG. 20 is a TEM photograph showing a cross section of a nanoporous fiber of Example 12.
FIG. 21 is a TEM photograph showing a cross section of a polymer alloy fiber of Example 15.
FIG. 22 is a TEM photograph showing a cross section of a nanoporous fiber of Example 15.
FIG. 23 is a view showing a spinning device.
FIG. 24 is a view showing a base.
FIG. 25 is a view showing a stretching device.
FIG. 26 is a view showing a spinning device.
FIG. 27 is a view showing a stretch false twisting apparatus.
FIG. 28 is a view showing a direct spinning apparatus.
[Explanation of symbols]
1: Hopper
2: Melting part
3: Spinning pack
4: Base
5: Chimney
6: Thread
7: Focusing refueling guide
8: First take-up roller
9: Second take-up roller
10: winding yarn
11: Measurement section
12: Discharge hole length
13: Discharge hole diameter
14: undrawn yarn
15: Feed roller
16: 1st hot roller
17: Second hot roller
18: Delivery roller (room temperature)
19: drawn yarn
20: Static kneader
21: undrawn yarn
22: Feed roller
23: heater
24: cooling plate
25: Rotor
26: Delivery roller
27: False twisted yarn
28: 1st hot roller
29: Second hot roller

Claims (10)

A nanoporous fiber having pores having a diameter of 100 nm or less, wherein the area ratio of pores having a diameter of 200 nm or more to the entire fiber cross section is 1.5% or less. The nanoporous fiber according to claim 1, wherein the average diameter of the pores is 0.1 to 50 nm. 3. The nanoporous fiber according to claim 1, wherein the area ratio of pores having a diameter of 50 nm or more to the entire fiber cross section is 1.5% or less. The nanoporous fiber according to any one of claims 1 to 3, wherein the strength is 1.5 cN / dtex or more. The nanoporous fiber according to any one of claims 1 to 4, comprising at least 80% by weight of polyester or polyamide. The nanoporous fiber according to any one of claims 1 to 5, having a moisture absorption (ΔMR) of 4% or more. The nanoporous fiber according to any one of claims 1 to 6, which has reversible water swellability and has a swelling ratio in the yarn longitudinal direction of 6% or more. The nanoporous fiber according to any one of claims 1 to 7, wherein at least a part of the nanoporous fiber is fibrillated, and the fibril diameter is 0.001 to 5 µm. The nanoporous fiber according to any one of claims 1 to 8, wherein the area of the nanoporous portion is 5 to 95% with respect to the fiber cross section. A fiber product having at least a portion of the nanoporous fiber according to any one of claims 1 to 9.

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