JP4698930B2 - Fiber structures containing nanofibers - Google Patents

Description

【００８３】
【表２】

【００８４】
（実施例５）
実施例１で用いたＮ６と共重合ＰＥＴを、図１５の装置を用いて別々に２７０℃で溶融した後、１軸混練器２１を通してポリマー融液を紡糸温度２８０℃のスピンブロック３に導いた。そして、紡糸パック４内に装着した静止混練器２２（東レエンジニアリング社製商品名“ハイミキサー”）を用いて２種のポリマーを１０４万分割して十分混合した後、実施例と１同様に溶融紡糸を行った。このときのポリマーのブレンド比は、Ｎ６が２０重量％、共重合ＰＥＴが８０重量％であった。この未延伸糸に実施例１と同様に延伸・熱処理を施した。得られたポリマーアロイ繊維は、１２０ｄｔｅｘ、３６フィラメント、強度３．９ｃＮ／ｄｔｅｘ、伸度３８％、Ｕ％＝１．７％の優れた特性を示した。このポリマーアロイ繊維の横断面をＴＥＭで観察したところ、実施例１同様、共重合ＰＥＴが海、Ｎ６が島の海島構造を示し、島Ｎ６の数平均による直径は５２ｎｍであり、Ｎ６が超微分散化したポリマーアロイ繊維が得られた。
【００８５】
ここで得られたポリマーアロイ繊維を用いて実施例と１同様に、アルカリ処理により紡績糸形状のナノファイバー集合体からなる目付６０ｇ／ｍ²の丸編み地を得た。さらにこれらのナノファイバーの単繊維繊度ばらつきを実施例１同様に解析した結果、ナノファイバーの数平均による単繊維直径は５４ｎｍ（３×１０^-5ｄｔｅｘ）と従来にない細さであり、単繊維繊度ばらつきも非常に小さいものであった（表４参照。）。
【００８６】
また、このナノファイバー集合体からなる丸編み地の吸湿率（ΔＭＲ）は６％であった。また、このＮ６ナノファイバー集合体からなる糸は、強度２．０ｃＮ／ｄｔｅｘ、伸度５０％であった。さらに１４０℃乾熱での収縮率は３％であった。さらに、この丸編み地にバフィングを施したところ、従来の超極細繊維では到達し得なかった超ピーチ感や人肌のようなしっとりとしたみずみずしい優れた風合いを示した。また、バフィングを施していない丸編み地をシルコートＰＰ（特殊変性シリコーン／松本油脂（株）製商品名）の１０ｗｔ％水溶液に浸漬し、水溶液のピックアップ率が１５０％となるよう処理液を丸編み地に付与した。処理液を付与後、１１０℃で３分間、リラックス状態でオーブン中で乾燥した。乾燥後、揉布処理を行ったところ、バフィングとはまた異なる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た。さらに接触冷感もあるものであった。また、これらの丸編み地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、良好な寸法安定性を示した。
【００８７】
（実施例６）
実施例１で用いたＮ６と共重合ＰＥＴを、図１６の装置を用いて２７０℃の２軸押出混練機２３で溶融混練した後、ポリマー融液を紡糸温度２８０℃のスピンブロック３に導いた。そして、実施例１同様に溶融紡糸を行った。このときのポリマーのブレンド比はＮ６が２０重量％、共重合ＰＥＴが８０重量％であった。この未延伸糸に実施例１同様に延伸・熱処理を施した。得られたポリマーアロイ繊維は、１２０ｄｔｅｘ、３６フィラメント、強度３．９ｃＮ／ｄｔｅｘ、伸度３８％、Ｕ％＝１．７％の優れた特性を示した。このポリマーアロイ繊維の横断面をＴＥＭで観察したところ、実施例１と同様、共重合ＰＥＴが海、Ｎ６が島の海島構造を示し、島Ｎ６の数平均による直径は５４ｎｍであり、Ｎ６が超微分散化したポリマーアロイ繊維が得られた。
【００８８】
ここで得られたポリマーアロイ繊維を用いて実施例と１同様に、アルカリ処理により紡績糸形状のナノファイバー集合体からなる目付６０ｇ／ｍ²の丸編みを得た。さらにこれらのナノファイバーの単繊維繊度ばらつきを実施例１同様に解析した結果、ナノファイバーの数平均による単繊維直径は５６ｎｍ（３×１０^-5ｄｔｅｘ）と従来にない細さであり、単繊維繊度ばらつきも非常に小さいものであった（表４参照。）。
【００８９】
また、このナノファイバー集合体からなる丸編み地の吸湿率（ΔＭＲ）は６％であった。また、このＮ６ナノファイバー集合体からなる糸は、強度２．０ｃＮ／ｄｔｅｘ、伸度５０％であった。さらに１４０℃乾熱での収縮率は３％であった。さらに、この丸編み地にバフィングを施したところ、従来の超極細繊維では到達し得なかった超ピーチ感や人肌のようなしっとりとしたみずみずしい優れた風合いを示した。また、バフィングを施していない丸編み地をシルコートＰＰ（特殊変性シリコーン／松本油脂（株）製商品名）の１０ｗｔ％水溶液に浸漬し、水溶液のピックアップ率が１５０％となるよう処理液を丸編に付与した。処理液を付与後、１１０℃で３分間、リラックス状態でオーブン中で乾燥した。乾燥後、揉布処理を行ったところ、バフィングとはまた異なる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た。さらに接触冷感もあるものであった。
【００９０】
また、これらの丸編み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、良好な寸法安定性を示した。
【００９１】
【表３】

【００９２】
【表４】

【００９３】
（実施例７）
共重合ＰＥＴをポリアルキレングリコール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登録商標“パオゲンＰＰ−１５”（溶融粘度３５００ｐｏｉｓｅ、２６２℃、１２１．６ｓｅｃ^-1、融点５５℃）に代え、口金孔壁とポリマーの間の剪断応力を０．０７５ＭＰａ、紡糸速度を５０００ｍ／分として、実施例１と同様に混練し、溶融紡糸を行った。得られたポリマーアロイ繊維は、７０ｄｔｅｘ、３６フィラメント、強度３．８ｃＮ／ｄｔｅｘ、伸度５０％、Ｕ％＝１．７％の優れた特性を示した。このポリマーアロイ繊維の横断面をＴＥＭで観察したところ、熱水可溶性ポリマーが海、Ｎ６が島の海島構造を示し、島Ｎ６の数平均による直径は５３ｎｍであり、Ｎ６が超微分散化したポリマーアロイ繊維が得られた。
【００９４】
ここで得られたポリマーアロイ繊維を用いて実施例１同様に、アルカリ処理により目付６０ｇ／ｍ²のＮ６ナノファイバー集合体からなる丸編み地を得た。さらにこれらのナノファイバーの単繊維繊度ばらつきを実施例１同様に解析した結果、ナノファイバーの数平均による単繊維直径は５６ｎｍ（３×１０^-5ｄｔｅｘ）と従来にない細さであり、単繊維繊度ばらつきも非常に小さいものであった（表６参照。）。また、このナノファイバー集合体からなる丸編み地の吸湿率（ΔＭＲ）は６％であった。また、このＮ６ナノファイバー集合体からなる糸は、強度２．０ｃＮ／ｄｔｅｘ、伸度６０％であった。
【００９５】
さらに、この丸編み地にバフィングを施したところ、従来の超極細繊維では到達し得なかった超ピーチ感や人肌のようなしっとりとしたみずみずしい優れた風合いを示した。また、バフィングを施していない丸編み地をシルコートＰＰ（特殊変性シリコーン／松本油脂（株）製商品名）の１０ｗｔ％水溶液に浸漬し、水溶液のピックアップ率が１５０％となるよう処理液を丸編み地に付与した。処理液を付与後、１１０℃で３分間、リラックス状態でオーブン中で乾燥した。乾燥後、揉布処理を行ったところ、バフィングとはまた異なる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た。さらに接触冷感もあるものであった。また、これらの丸編み地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良好な寸法安定性を示した。
【００９６】
（実施例８）
Ｎ６の代わりに、溶融粘度１０００ｐｏｉｓｅ（２８０℃、１２１．６ｓｅｃ^-1）、融点２５０℃のＮ６６を用い、図１５の装置を用いてＮ６６を２７０℃、実施例７で用いた熱水可溶性ポリマーを８０℃で溶融した後、ポリマー融液を紡糸温度を２８０℃のスピンブロック３に導いた。そして、実施例と５同様に溶融紡糸を行った。このときのポリマーのブレンド比はＮ６６が２０重量％、熱水可溶性ポリマーが８０重量％、単孔あたりの吐出量は１．０ｇ／分とした。このときの紡糸速度は５０００ｍ／分、口金孔壁とポリマーの間の剪断応力は０．０６２ＭＰａと充分低いものであった。そして、７０ｄｔｅｘ、３６フィラメント、強度４．５ｃＮ／ｄｔｅｘ、伸度４５％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横断面をＴＥＭで観察したところ、熱水可溶性ポリマーが海、Ｎ６６が島の海島構造を示し、島Ｎ６６の数平均による直径は５８ｎｍであり、Ｎ６６が超微分散化したポリマーアロイ繊維が得られた。
【００９７】
ここで得られたポリマーアロイ繊維を用いて実施例と１同様に、アルカリ処理により目付６０ｇ／ｍ²のＮ６ナノファイバー集合体からなる丸編み地を得た。さらにこれらのナノファイバーの単繊維繊度ばらつきを実施例１同様に解析した結果、ナノファイバーの数平均による単繊維直径は６２ｎｍ（３×１０^-5ｄｔｅｘ）と従来にない細さであり、単繊維繊度ばらつきも非常に小さいものであった（表６参照。）。
【００９８】
また、このナノファイバー集合体からなる丸編み地の吸湿率（ΔＭＲ）は６％であった。また、このＮ６ナノファイバー集合体からなる糸は、強度２．５ｃＮ／ｄｔｅｘ、伸度６０％であった。さらに、この丸編み地にバフィングを施したところ、従来の超極細繊維では到達し得なかった超ピーチ感や人肌のようなしっとりとしたみずみずしい優れた風合いを示した。また、バフィングを施していない丸編み地をシルコートＰＰ（特殊変性シリコーン／松本油脂（株）製商品名）の１０ｗｔ％水溶液に浸漬し、水溶液のピックアップ率が１５０％となるよう処理液を丸編み地に付与した。処理液を付与後、１１０℃で３分間、リラックス状態でオーブン中で乾燥した。乾燥後、揉布処理を行ったところ、バフィングとはまた異なる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た。さらに接触冷感もあるものであった。また、これらの丸編み地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良好な寸法安定性を示した。
【００９９】
（実施例９）
溶融粘度３０００ｐｏｉｓｅ（２６２℃、１２１．６ｓｅｃ^-1）、融点２２５℃の共重合ＰＥＴ（ＰＥＧ１０００を８重量％、イソフタル酸を７ｍｏｌ％共重合）と実施例８で用いた熱水可溶性ポリマーを、実施例６と同様に混練、溶融紡糸した。このときのポリマーのブレンド比は共重合ＰＥＴが２０重量％、熱水可溶性ポリマーが８０重量％、単孔あたりの吐出量は１．０ｇ／分、紡糸速度は６０００ｍ／分とした。このときの口金孔壁とポリマーの間の剪断応力は０．０７８ＭＰａと十分低いものであった。そして、６０ｄｔｅｘ、３６フィラメント、強度３．０ｃＮ／ｄｔｅｘ、伸度５５％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横断面をＴＥＭで観察したところ、熱水可溶性ポリマーが海、共重合ＰＥＴが島の海島構造を示し、島共重合ＰＥＴの数平均による直径は５２ｎｍ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。
【０１００】
ここで得られたポリマーアロイ繊維を用いて実施例１同様に丸編み地作製後、１００℃の熱水で熱水可溶性ポリマーを溶出することにより、絹のような「きしみ感」やレーヨンのような「ドライ感」を有するナノファイバー集合体からなる目付６０ｇ／ｍ²の丸編み地を得た。そして、ナノファイバーの単繊維繊度ばらつきを実施例１同様に解析した結果、ナノファイバーの数平均による単繊維直径は５４ｎｍ（３×１０^-5ｄｔｅｘ）と従来にない細さであり、単繊維繊度ばらつきも非常に小さいものであった（表６参照。）。この共重合ＰＥＴナノファイバー集合体からなる丸編み地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、ナノファイバーにジエチレントリアミンを担持させた。これの硫化水素除去を評価したところ、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。また、この丸編み地を用いてＡ４サイズの消臭シートを作製し、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良好な寸法安定性を示した。
【０１０１】
（実施例１０）
溶融粘度１９００ｐｏｉｓｅ（２８０℃、１２１．６ｓｅｃ^-1）、融点２５５℃のＰＥＴと実施例７で用いた熱水可溶性ポリマーを、実施例９同様に混練、溶融紡糸した。このときのポリマーのブレンド比はＰＥＴが２０重量％、熱水可溶性ポリマーが８０重量％、ＰＥＴの溶融温度は２８５℃、熱水可溶性ポリマーの溶融温度は８０℃、単孔あたりの吐出量は１．０ｇ／分とした。このときの口金孔壁とポリマーの間の剪断応力は０．０８０ＭＰａと十分低いものであった。そして、６０ｄｔｅｘ、３６フィラメント、強度３．０ｃＮ／ｄｔｅｘ、伸度４５％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横断面をＴＥＭで観察したところ、熱水可溶性ポリマーが海、ＰＥＴが島の海島構造を示し、島ＰＥＴの数平均による直径は６２ｎｍであり、ＰＥＴが超微分散化したポリマーアロイ繊維が得られた。
【０１０２】
ここで得られたポリマーアロイ繊維を用いて、実施例９と同様の操作により、ナノファイバー集合体からなる目付６０ｇ／ｍ²の丸編み地を得た。このナノファイバーの数平均による単糸直径は６５ｎｍ（３×１０^-5ｄｔｅｘ）と従来にない細さであり、単糸繊度ばらつきも非常に小さいものであった（表６参照。）。このＰＥＴナノファイバー集合体からなる丸編み地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、ナノファイバーにジエチレントリアミンを担持させた。これの硫化水素除去を評価したところ、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。また、この丸編み地を用いてＡ４サイズの消臭シートを作製し、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良好な寸法安定性を示した。
【０１０３】
（実施例１１）
溶融粘度１２００ｐｏｉｓｅ（２６２℃、１２１．６ｓｅｃ^-1）、融点２２５℃のＰＢＴと実施例７で用いた熱水可溶性ポリマーを、実施例９同様に混練、溶融紡糸した。このときのポリマーのブレンド比はＰＥＴが２０重量％、熱水可溶性ポリマーが８０重量％、ＰＢＴの溶融温度は２５５℃、熱水可溶性ポリマーの溶融温度は８０℃、紡糸温度は２６５℃、単孔あたりの吐出量は１．０ｇ／分とした。このときの口金孔壁とポリマーの間の剪断応力は０．０７５ＭＰａと十分低いものであった。そして、６０ｄｔｅｘ、３６フィラメント、強度３．０ｃＮ／ｄｔｅｘ、伸度４５％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横断面をＴＥＭで観察したところ、熱水可溶性ポリマーが海、ＰＢＴが島の海島構造を示し、島ＰＢＴの数平均による直径は６２ｎｍであり、ＰＢＴが超微分散化したポリマーアロイ繊維が得られた。
【０１０４】
ここで得られたポリマーアロイ繊維を用いて、実施例９と同様の操作により、ナノファイバー集合体からなる目付６０ｇ／ｍ²の丸編み地を得た。このナノファイバーの数平均による単繊維直径は６５ｎｍ（４×１０^-5ｄｔｅｘ）と従来にない細さであり、単繊維繊度ばらつきも非常に小さいものであった（表６参照。）。このＰＢＴナノファイバー集合体からなる丸編み地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、ナノファイバーにジエチレントリアミンを担持させた。これの硫化水素除去を評価したところ、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。また、この丸編み地を用いてＡ４サイズの消臭シートを作製し、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良好な寸法安定性を示した。
【０１０５】
（実施例１２）
溶融粘度２２００ｐｏｉｓｅ（２６２℃、１２１．６ｓｅｃ^-1）、融点２２５℃のＰＴＴと実施例７で用いた熱水可溶性ポリマーを、実施例９同様に混練、溶融紡糸した。このときの口金孔壁とポリマーの間の剪断応力は０．０７３ＭＰａと十分低いものであった。そして、６０ｄｔｅｘ、３６フィラメント、強度３．０ｃＮ／ｄｔｅｘ、伸度４５％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横断面をＴＥＭで観察したところ、熱水可溶性ポリマーが海、ＰＴＴが島の海島構造を示し、島ＰＴＴの数平均による直径は６２ｎｍであり、ＰＴＴが超微分散化したポリマーアロイ繊維が得られた。
【０１０６】
ここで得られたポリマーアロイ繊維を用いて、実施例９と同様の操作により、ナノファイバー集合体からなる目付６０ｇ／ｍ²の丸編み地を得た。このナノファイバーの数平均による単繊維直径は６５ｎｍ（４×１０^-5ｄｔｅｘ）と従来にない細さであり、単繊維繊度ばらつきも非常に小さいものであった（表６参照。）。このＰＴＴナノファイバー集合体からなる丸編み地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、ナノファイバーにジエチレントリアミンを担持させた。これの硫化水素除去を評価したところ、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。また、この丸編み地を用いてＡ４サイズの消臭シートを作製し、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良好な寸法安定性を示した。
【０１０７】
（実施例１３）
溶融粘度３５００ｐｏｉｓｅ（２２０℃、１２１．６ｓｅｃ^-1）、融点１７０℃のＰＬＡと実施例７で用いた熱水可溶性ポリマーを、実施例９同様に混練し、溶融紡糸した。このときのポリマーのブレンド比はＰＬＡが２０重量％、熱水可溶性ポリマーが８０重量％、紡糸温度２３５℃、口金面温度２２０℃、単孔あたりの吐出量は１．０ｇ／分とした。このときの口金孔壁とポリマーの間の剪断応力は０．０８０ＭＰａと十分低いものであった。そして、６０ｄｔｅｘ、３６フィラメント、強度２．５ｃＮ／ｄｔｅｘ、伸度３５％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横断面をＴＥＭで観察したところ、熱水可溶性ポリマーが海、ＰＬＡが島の海島構造を示し、島ＰＬＡの数平均による直径は４８ｎｍであり、ＰＬＡが超微分散化したポリマーアロイ繊維が得られた。
【０１０８】
ここで得られたポリマーアロイ繊維を用いて、実施例９と同様の操作により、ナノファイバー集合体からなる目付６０ｇ／ｍ²の丸編み地を得た。このナノファイバーの数平均による単糸直径は５０ｎｍ（２×１０^-5ｄｔｅｘ）と従来にない細さであり、単糸繊度ばらつきも非常に小さいものであった（表６参照。）。このＰＬＡナノファイバー集合体からなる丸編み地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、ナノファイバーにジエチレントリアミンを担持させた。これの硫化水素除去を評価したところ、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。また、この丸編み地を用いてＡ４サイズの消臭シートを作製し、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、良好な寸法安定性を示した。
【０１０９】
【表５】

【０１１０】
【表６】

【０１１１】
（比較例７）
比較例１で作製したＰＳ／ＰＥＴ海島複合糸を用いて丸編み地を作製し、比較例１と同様にＰＳを除去し、単繊維繊度０．０４ｄｔｅｘのＰＥＴ超極細糸からなる丸編み地（目付１５０ｇ／ｍ²）を得た。このＰＥＴ超極細糸からなる丸編み地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、ＰＥＴ超極細糸にジエチレントリアミンを担持させたが、ほとんど坦持できなかった。これの硫化水素除去を評価したところ、１０分間で３０ｐｐｍから１５ｐｐｍまでしか濃度が低下せず硫化水素除去能力が不十分であった。
【０１１２】
（実施例１４）
実施例２で作製したシリコーン処理された目付１５０ｇ／ｍ²のＮ６ナノファイバーからなる丸編み地を用いてＴシャツを作製したが、人肌のようなタッチのため非常に快適で、しかもヒーリング効果もあるものであった。また、これ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良好な寸法安定性を示した。
【０１１３】
（実施例１５）
実施例３で作製したシリコーン処理された目付１００ｇ／ｍ²のＮ６ナノファイバーからなる丸編み地を用いて女性用のショーツを作製したが、人肌のようなタッチのため非常に快適で、しかもヒーリング効果もあるものであった。また、これ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良好な寸法安定性を示した。
【０１１４】
（実施例１６）
実施例４で作製したシリコーン処理された目付１５０ｇ／ｍ²のＮ６ナノファイバーからなる織物を用いて女性用のシャツを作製したが、人肌のようなタッチのため非常に快適で、しかもヒーリング効果もあるものであった。また、これ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良好な寸法安定性を示した。
した。
【０１１５】
（実施例１７）
実施例１および実施例２で作製したＮ６ナノファイバーからなる丸編み地および実施例４で作製した織物を用いて、Ａ４サイズの消臭シートを作製し、有害・悪臭物質ガスの除去試験としてアンモニア、酢酸および硫化水素の消臭試験を行ったところ、通常繊度のナイロン糸（４４ｄｔｅｘ、１２フィラメント）に比べ、優れた消臭能力（有害物質吸着能力）を示した（表７〜表９参照。）。
【０１１６】
【表７】

【０１１７】
【表８】

【０１１８】
【表９】

【０１１９】
（実施例１８）
実施例３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、東レ（株）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３と同様にアルカリ処理を行いナノ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／ｍ²でああり、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９０％と１０％であった。これをシルコートＰＰ（特殊変性シリコーン／松本油脂（株）製商品名）の１０ｗｔ％水溶液に浸漬し、水溶液のピックアップ率が１５０％となるように処理液を編み地に付与した。処理液を付与後、１１０℃で３分間、リラックス状態でオーブン中で乾燥した。乾燥後、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。このタイツは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。
【０１２０】
（実施例１９）
第１引き取りローラー９の速度（紡糸速度）を３５００ｍ／分として実施例２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を得た。このポリマーアロイ繊維の強度は２．５ｃＮ／ｄｔｅｘ、伸度は１００％、Ｕ％は１．９％であった。そして、これに図１８の装置を用いて延伸仮撚りを施し、３３３ｄｔｅｘ、９６フィラメントの仮撚り加工糸を得た。このとき回転子３３としてウレタンディスクを使用し、ヒーター３１の温度を１８０℃、延伸倍率を１．２倍とした。得られた仮撚り加工糸は、強度３．０ｃＮ／ｄｔｅｘ、伸度３２％であった。
【０１２１】
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ナノファイバーからなる目付１５０ｇ／ｍ²のカーテン用生地を得た。さらに、これらのナノファイバーの単繊維繊度ばらつきを実施例１同様に解析した結果、ナノファイバーの数平均による単繊維直径は８６ｎｍ（６×１０^-5ｄｔｅｘ）と従来にない細さであり、また、単繊維繊度が１×１０^-7〜１×１０^-4ｄｔｅｘの繊度比率は７８％であり、特に単繊維直径で７５〜１０４ｎｍの間に入る単繊維繊度比率は６４％であり、単繊維繊度ばらつきはごく小さいものであった。また、このＮ６ナノファイバー仮撚り加工糸は、強度２．０ｃＮ／ｄｔｅｘ、伸度４０％であった。
【０１２２】
また、このカーテン生地に実施例２同様にシリコーン処理を施したところ、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た。さらに接触冷感もあるものであった。また、これの吸湿率（ΔＭＲ）は６％と十分な吸湿性を示し、酢酸の消臭試験を行ったところ１０分間で濃度が１００ｐｐｍから１ｐｐｍまで低下し、優れた消臭性を示した。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、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。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、良好な寸法安定性を示した。
【０１２３】
（実施例２０）
実施例２で用いたＮ６／共重合ＰＥＴアロイポリマーと同じく実施例２で用いた溶融粘度５０００ｐｏｉｓｅ（２６２℃、剪断速度１２１．６ｓｅｃ^-1）、融点２２０℃のＮ６を別々に溶融し、吐出孔をＹ型とした口金を用いて芯鞘複合紡糸を実施例２と同様に行った。このとき、芯成分をアロイポリマー、鞘成分をＮ６とし、芯成分複合比を５０重量％とした。紡出糸は８００ｍ／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５．２ｃＮ／ｄｔｅｘ、伸度は２５％であった。
【０１２４】
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／ｍ² 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ナノファイバーがＮ６に包まれた構造を発現させた。また、得られたＮ６ナノファイバーの数平均による単繊維直径は８６ｎｍ（６×１０^-4ｄｔｅｘ）であり、また、単繊維繊度が１×１０^-7〜１×１０^-4ｄｔｅｘの繊度比率は７８％であり、特に単繊維直径で７５〜１０４ｎｍの間に入る単繊維繊度比率は６４％であり、単繊維繊度ばらつきはごく小さいものであった。これにより、カットパイル部分の目付は１２００ｇ／ｍ² となり、Ｎ６ナノファイバーの重量分率はカットパイル部分に対しては３３重量％、カーペット全体に対しては１５重量％であった。このカーペットは、カットパイル部分が鞘成分Ｎ６によりＮ６ナノファイバーを保持してるため毛倒れ性に問題はないものであった。また、カーペット全体に対してＮ６ナノファイバーが１５重量％含有されているため、十分な調湿性・消臭性を示し、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。
【０１２５】
（実施例２１）
実施例１９で得られたＮ６／共重合ＰＥＴアロイ仮撚加工糸を４本合糸した後、これを経糸と緯糸に用い、２／２ツイル織物を製織し、その後、実施例２１と同様にアルカリ処理することにより、Ｎ６ナノファイバー仮撚り加工糸からなる目付２００ｇ／ｍ²のインテリア用シート表皮を作製した。さらに、ＮＮ６ナノファイバーの単繊維繊度ばらつきを実施例１同様に解析した結果、ナノファイバーの数平均による単繊維直径は８６ｎｍ（６×１０^-5ｄｔｅｘ）と従来にない細さであり、また、単繊維繊度が１×１０^-7〜１×１０^-4ｄｔｅｘの繊度比率は７８％であり、特に単繊維直径で７５〜１０４ｎｍの間に入る単繊維繊度比率は６４％であり、単繊維繊度ばらつきはごく小さいものであった。これを椅子の表皮に用いたところ、風合いがソフトで快適であるだけでなく、十分な調湿性・消臭性を示し、爽やかな室内環境とすることができるものであった。
【０１２６】
（実施例２２）
実施例２で用いたＮ６／共重合ＰＥＴアロイポリマーと同じく、実施例２で用いた溶融粘度５０００ｐｏｉｓｅ（２６２℃、剪断速度１２１．６ｓｅｃ^-1）、融点２２０℃のＮ６を別々に溶融し、丸孔口金を用いて芯鞘複合紡糸を実施例２と同様に行った。このとき、芯成分をアロイポリマー、鞘成分をＮ６とし、芯成分複合比を３０重量％とした。これを１６００ｍ／分で引き取り一旦巻き取った後、第１ホットローラー１７の温度を９０℃、第２ホットローラー１８の温度を１３０℃、延伸倍率を２．７倍として延伸した。得られたポリマーアロイ繊維は２２０ｄｔｅｘ、１４４フィラメント、強度＝４．８ｃＮ／ｄｔｅｘ、伸度＝３５％、Ｕ％＝１．９％であった。そして、これに３００ターン／ｍの甘撚りを施し、経緯使いで平織物を作製した。そして、実施例２と同様にアルカリ処理を施し、Ｎ６ナノファイバーが鞘成分Ｎ６で覆われた繊維から成る目付２２０ｇ／ｍ²の織物を得た。また、得られたＮ６ナノファイバーの数平均による単繊維直径は８６ｎｍ（６×１０^-4ｄｔｅｘ）であり、また、単繊維繊度が１×１０^-7〜１×１０^-4ｄｔｅｘの繊度比率は７８％であり、特に単繊維直径で７５〜１０４ｎｍの間に入る単繊維繊度比率は６４％であり、単繊維繊度ばらつきはごく小さいものであった。さらに、これに実施例２と同様にシリコーン処理を施したところ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た。そして、これを用いて布団カバーとシーツを作製したが、優れた風合いと吸湿性のため非常に快適なものであった。さらに、優れた消臭性のため失禁等があっても臭いを抑えることができた。また、これらの寝装具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、良好な寸法安定性を示した。
【０１２７】
（実施例２３）
第１引き取りローラー９の速度を３５００ｍ／分として、実施例２２と同様に芯鞘複合紡糸を行い、２６４ｄｔｅｘ、１４４フィラメントのＮ６／共重合ＰＥＴポリマーアロイ繊維を得た。このポリマーアロイ繊維の強度は３．５ｃＮ／ｄｔｅｘ、伸度は１１０％、Ｕ％は１．９％であった。そして、これに図１８図１１の装置を用いて延伸仮撚りを施し、２２０ｄｔｅｘ、１４４フィラメントの仮撚り加工糸を得た。このとき、回転子３３としてウレタンディスクを使用し、ヒーター３１の温度を１８０℃、延伸倍率を１．２倍とした。得られた仮撚り加工糸は強度４．１ｃＮ／ｄｔｅｘ、伸度３２％であった。
【０１２８】
この仮撚り加工糸に３００ターン／ｍの甘撚りを施し、これを経糸および緯糸に用いて平織物を作製した。そしてこれに実施例１と同様にアルカリ処理を施し、Ｎ６ナノファイバーからなる目付１００ｇ／ｍ²のＮ６ナノファイバーが鞘成分Ｎ６で覆われた繊維からなる織物を得た。さらに、これらのナノファイバーの単繊維繊度ばらつきを実施例１同様に解析した結果、ナノファイバーの数平均による単繊維直径は８６ｎｍ（６×１０^-5ｄｔｅｘ）と従来にない細さであり、また、単繊維繊度が１×１０^-7〜１×１０^-4ｄｔｅｘの繊度比率は７８％であり、特に単繊維直径で７５〜１０４ｎｍの間に入る単繊維繊度比率は６４％であり、単繊維繊度ばらつきはごく小さいものであった。この織物はＮ６中空糸中によりＮ６ナノファイバーがカプセル化された構造となり、マシュマロのような柔らかで弾力性のある優れた風合いを示した。また、このＮ６ナノファイバーを含む仮撚り加工糸は、強度２．９ｃＮ／ｄｔｅｘ、伸度４１％であった。
【０１２９】
また、この織物に実施例２同様にシリコーン処理を施したところ、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た。さらに接触冷感もあるものであった。また、これの吸湿率（ΔＭＲ）は６％と十分な吸湿性を示した。そして、この織物を用いて女性用のシャツを作製したが、非常に快適であり、ヒーリング効果もあるものであった。このシャツを家庭用洗濯機で洗濯ネットに入れずに洗濯・脱水したが、形くずれは発生せず、Ｎ６ナノファイバーをＮ６中空糸でカプセル化することでさらに良好な寸法安定性を示した。
【０１３０】
（実施例２４）
実施例２で作製したポリマーアロイ繊維を経糸および緯糸に用いて平織物を作製した。そして、実施例２と同様にアルカリ処理を行い、ナノファイバー集合体からなる目付２５０ｇ／ｍ²の平織物を得た。さらにこれのナノファイバーの単繊維繊度ばらつきを実施例１同様に解析した結果、ナノファイバーの数平均による単繊維直径は８６ｎｍ（６×１０^-5ｄｔｅｘ）と従来にない細さであり、また、単繊維繊度が１×１０^-7〜１×１０^-4ｄｔｅｘの繊度比率は７８％であり、特に単繊維直径で７５〜１０４ｎｍの間に入る単繊維繊度比率は６４％であり、単繊維繊度ばらつきはごく小さいものであった。この織物は水に浸漬すると特異な粘着性を示すものであった。そして、これにバフィングを施した。これは、従来の極細糸を用いたワイピングクロスよりも拭き取り性が良く、ワイピングクロスとして好適なものであった。また、これ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、良好な寸法安定性を示した。
【０１３１】
（実施例２５）
実施例２で作製したポリマーアロイ繊維に機械捲縮を施した後、繊維長５１ｍｍにカットし、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、ニードルパンチを用い、目付７５０ｇ／ｍ²の繊維絡合不織布とした。さらに、ポリエーテル系ポリウレタン（ＰＵ）を主体とする１３重量％のポリウレタン組成物（ＰＵ）と８７重量％のＮ，Ｎ’−ジメチルホルムアミド（ＤＭＦ）からなる液を繊維絡合不織布に含浸させ、ＤＭＦ４０重量％水溶液中でＰＵを凝固後、水洗した。さらに、この不織布に３％の水酸化ナトリウム水溶液（６０℃、浴比１：１００）でアルカリ処理を２時間施し、共重合ＰＥＴの９９％以上を除去し、ＰＵ含有率が４０重量％のＮ６ナノファイバー集合体とＰＵからなるナノファイバー構造体からなる研磨基材を得た。さらに、これのナノファイバーの単繊維繊度ばらつきを実施例１同様に解析した結果、ナノファイバーの数平均による単繊維直径は８６ｎｍ（６×１０^-5ｄｔｅｘ）と従来にない細さであり、また、単繊維繊度が１×１０^-7〜１×１０^-4ｄｔｅｘの繊度比率は７８％であり、特に単繊維直径で７５〜１０４ｎｍの間に入る単繊維繊度比率は６４％であり、単繊維繊度ばらつきはごく小さいものであった。研磨基材中のＮ６ナノファイバーの含量は７０重量％、Ｎ６ナノファイバー不織布の目付は３２５ｇ／ｍ²であった。これを２分割するように切断した後、表面をＪＩＳ＃２４０、＃３５０、＃５００番のサンドペーパーでバフイングした。さらに、これを隙間が１．０ｍｍの表面温度１５０℃の上下２本のフッ素加工した加熱ローラーでニップし、０．７ｋｇ／ｃｍ²の圧力でプレスした後、表面温度１５℃の冷却ローラーで急冷し表面を平滑化した研磨布を得た。そして、この研磨布を以下の方法で評価した結果を表１０に示すが、従来超極細糸を用いたものに比べ被研磨物の平滑性が高くまた欠点であるスクラッチ数も少なく、優れた研磨特性を示した。さらに、目付が十分大きいため研磨時の研磨布の破れも無く、加工性も良好であった。
【０１３２】
＜研磨評価：ハードディスクのテキスチャリング＞
被研磨物：市販アルミニウム板にＮｉ−Ｐメッキ後ポリッシュ加工した基板
（平均表面粗さ＝０．２８ｎｍ）
研磨条件：以下の条件で、該基板をテキスチャー装置に取り付け研磨を行った。 砥粒 ：平均粒径０．１μｍダイヤモンドの遊離砥粒スラリー
滴下速度 ：４．５ｍｌ／分
回転数 ：１０００ｒｐｍ
テープ速度：６ｃｍ／分
研磨条件 ：振幅１ｍｍ−横方向振動３００回／分
評価枚数 ：該基板３０枚／水準
＜被研磨物の平均表面粗さＲａ＞
温度２０℃、相対湿度５０％のクリーン室に設置された防音装置付きのＶｅｅｃｏ社製原糸間力顕微鏡（ＡＦＭ）を用いて、基板３０枚／水準の表面粗さを測定し、その平均表面粗さＲａを求める。測定範囲は、各基板のディスク中心を基準とし半径の中央点２カ所を対称に選定し、各点５μｍ×５μｍの広さで測定を行う。
【０１３３】
＜スクラッチ数＞
ＺＹＧＯ社製干渉型顕微鏡で表面観察し、各サンプルの表面スクラッチ数（Ｘ）を測定する。スクラッチは、０．１μｍ×１００μｍ以上の大きさのものをカウントする。これを基板３０枚／水準測定し、傷の数による点数ｙからスクラッチ数βを定義する。
Ｘ≦４のとき ｙ＝Ｘ
Ｘ≧５のとき ｙ＝５
β＝Σｙ_i （ｉ＝１〜３０）
ここでΣｙ_iは、サンプル３０枚分のスクラッチ総数である。
【０１３４】
（比較例８）
不織布作成時のウエッブの密度を甘くすることによりＮ６ナノファイバーの目付を１５ｇ／ｍ²（繊維絡合不織布の目付を３０ｇ／ｍ²）として、実施例２５と同様に研磨布を作製し研磨試験を行ったが、目付が小さすぎるため研磨時に破れが発生するトラブルがあった。
【０１３５】
（比較例９）
比較例３で作製したＮ６／ＰＥブレンド繊維に機械捲縮を施した後、繊維長５１ｍｍにカットし、カードで開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、ニードルパンチを用い、目付５００ｇ／ｍ²の繊維絡合不織布とした。さらにポリエーテル系ポリウレタン（ＰＵ）を主体とする１３重量％のポリウレタン組成物と８７重量％のＮ，Ｎ’−ジメチルホルムアミド（ＤＭＦ）からなる液を含浸させ、ＤＭＦ４０重量％水溶液中でＰＵを凝固後、水洗した。さらに、この不織布にパークレン処理を行い、Ｎ６超極細糸とＰＵからなるナノファイバー構造体からなる研磨基材を得た。これを用い、実施例２５と同様の操作により研磨布を得た。そして、この研磨布の評価を行ったが、Ｒａ＝１．６ｎｍ、β＝３２とナノファイバー集合体を用いたものに比べ被研磨物の平滑性が低くまた欠点であるスクラッチ数も多くなり、劣った研磨特性を示した。結果を表１０に示す。
【０１３６】
【表１０】

【０１３７】
（実施例２６）
実施例１および実施例２、５、６で作製したポリマーアロイ繊維に機械捲縮を施した後、繊維長５１ｍｍにカットし、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を用い、目付７５０ｇ／ｍ²の繊維絡合不織布とした。さらに、ポリエーテル系ポリウレタン（ＰＵ）を主体とする１３重量％のポリウレタン組成物と８７重量％のＮ，Ｎ’−ジメチルホルムアミド（ＤＭＦ）からなる液を含浸させ、ＤＭＦ４０重量％水溶液中でＰＵを凝固後、水洗した。さらに、この不織布に３％の水酸化ナトリウム水溶液（６０℃、浴比１：１００）でアルカリ処理を２時間施し、共重合ＰＥＴの９９％以上を除去し、Ｎ６ナノファイバー集合体とＰＵからなる厚さ約１ｍｍのナノファイバー構造体を得た。Ｎ６ナノファイバーの数平均直径は、それぞれ６０、８６、６１および６１ｎｍであった。この構造体中のＮ６ナノファイバーの含量は、それぞれ５０、７０、５０および５０重量％、Ｎ６ナノファイバー不織布の目付は、それぞれ１５０、３２５、１５０および１５０ｇ／ｍ²であった。この不織布の１面をサンドペーパーでバフィング処理して厚さを０．８ｍｍとした後、他面をエメリーバフ機で処理してナノファイバー集合体立毛面を形成し、さらに染色した後、仕上げを行いスエード調人工皮革を得た。得られた製品は、外観が極めて良好で染色斑もなく、力学特性にも問題はなかった。また、従来の超極細糸を用いた人工皮革に比べ、さらに柔らかできめの細かいタッチであった。また、吸湿性にも優れるため、従来の人工皮革では持ち得なかった人肌のようなみずみずしさも併せ持つ優れた風合いであった。
【０１３８】
（比較例１０）
比較例３で作製したＮ６／ＰＥブレンド繊維に機械捲縮を施した後、繊維長５１ｍｍにカットし、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、ニードルパンチを用い、目付５００ｇ／ｍ²の繊維絡合不織布とした。さらに、ポリエーテル系ポリウレタン（ＰＵ）を主体とする１３重量％のポリウレタン組成物と８７重量％のＮ，Ｎ’−ジメチルホルムアミド（ＤＭＦ）からなる液を含浸させ、ＤＭＦ４０重量％水溶液中でＰＵを凝固後、水洗した。さらに、この不織布にパークレン処理を行い、Ｎ６超極細糸とＰＵからなる厚さ約１ｍｍのナノファイバー構造体を得た。このナノファイバー構造体の１面をサンドペーパーでバフィング処理して厚さを０．８ｍｍとした後、他面をエメリーバフ機で処理してナノファイバー集合体立毛面を形成し、さらに染色した後、仕上げを行いスエード調人工皮革を得た。これの風合いは、単なるスエードの模造品であり従来の超極細繊維を用いた人工皮革を超えるものではなかった。
【０１３９】
（実施例２７）
実施例２で作製したポリマーアロイ繊維に機械捲縮を施した後、繊維長５１ｍｍにカットし、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を用い、目付４００ｇ／ｍ²の繊維絡合不織布とした後、３％の水酸化ナトリウム水溶液（６０℃、浴比１：１００）でアルカリ処理を２時間施し、共重合ＰＥＴの９９％以上を除去し、目付２００ｇ／ｍ²のＮ６ナノファイバー不織布を得た。得られたＮ６ナノファイバーの数平均による単繊維直径は８６ｎｍ（６×１０^-4ｄｔｅｘ）であり、また、単繊維繊度が１×１０^-7〜１×１０^-4ｄｔｅｘの繊度比率は７８％であり、特に単繊維直径で７５〜１０４ｎｍの間に入る単繊維繊度比率は６４％であり、単繊維繊度ばらつきはごく小さいものであった。これを直径４．７ｃｍの円形に切断したもの５枚を重ねて円形のフィルターカラムを作製し、白血球（５７００個／μリットル）を含む牛血を２ｍリットル／分の流速で通液したところ、圧力損失が１００ｍｍＨｇに達するまでの時間は１００分間であり、そのときの顆粒球除去率は９９％以上、リンパ球除去率は６０％と炎症性の白血球である顆粒球を選択できるものであった。これは、ナノファイバー同士の隙間による効果であると考えられる。また、目付が十分大きいため試験中のフィルター破れ等のトラブルは発生しなかった。
【０１４０】
（実施例２８）
実施例２７で作製したナノファイバー不織布０．５ｇをオートクレーブで減菌し、１５ｍリットルのエンドトキシンを含む牛血清で吸着能力の評価（３７℃、２時間）をしたところ、エンドトキシン濃度ＬＰＳが１０．０ｎｇ／ｍリットルから１．５ｎｇ／ｍリットルまで減少しており、優れた吸着能力を示した。これは、Ｎ６ナノファイバーは活性表面が通常のナイロン繊維に比べはるかに多いため、アミノ末端が通常よりもはるかに多く存在しているためと考えられる。
【０１４１】
（実施例２９）
実施例１３と同様のポリマーの組み合わせで、図１７の装置を用いてスパンボンド不織布を得た。すなわち、糸条７をイジェクター２５を通して開繊板２６に衝突させて開繊糸条２７とし、捕集装置２８で引き取り捕集した。このとき、２軸押出混練機２３での溶融温度は２２５℃、紡糸温度は２３０℃、口金面温度は２１７℃とした。また、口金は実施例１で用いたものと同スペックとし、単孔吐出量は０．８ｇ／分、口金下面から冷却開始までの距離は１２ｃｍとした。得られたポリマーアロイ不織布を６０℃の温水で２時間処理することにより、熱水可溶性ポリマーを９９％以上溶解除去し、ＰＬＡナノファイバーからなる目付２０ｇ／ｍ²の不織布を得た。この不織布のナノファイバー単繊維直径の数平均は５０ｎｍ（２×１０^-5ｄｔｅｘ）、繊度比率の９８％以上が単繊維繊度１×１０^-7〜１×１０^-4ｄｔｅｘの範囲に在り、ナノファイバーの単繊維直径が４５〜７４ｎｍの範囲にあるものの繊度比率が７０％であった。このＰＬＡ不織布は軽く、しかも使用に際して不織布の破れ等は発生せずラッピング用として好適であった。
【０１４２】
（実施例３０）
実施例１および実施例２で作製したナノファイバー集合体からなる丸編み地を、ヘキサメチレンジイソシアネートと分子量１０００のヘキサメチレンポリカーボネートからなるポリウレタンプレポリマー（分子量３０００〜４０００）の１５重量％水溶液に３０分間浸漬した。その後、丸編み地を引き上げ１２０℃、２０分間ポリウレタンプレポリマーを架橋させた。この操作により、ナノファイバー同士の空隙に侵入したポリウレタンプレポリマーが架橋反応により不溶化し、架橋ポリウレタンとＮ６ナノファイバーからなる複合体が生成した。得られた丸編み地形状の複合体は、大きなストレッチ性を有すると共に粘着質の得意な表面タッチを有するものであった。また、この複合体中のＮ６ナノファイバーの比率は、それぞれ５０重量％と６０重量％であった。
【０１４３】
（実施例３１）
実施例１および実施例２で作製したナノファイバー集合体からなる丸編み地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Ｎ６ナノファイバーの比率はそれぞれ４０、５０重量％であった
（実施例３２）
実施例９〜実施例１３で作製したポリエステルナノファイバー集合体からなる編地に、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、このポリエステルナノファイバー集合体への吸尽率は１０％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ポリエステル編地を得ることができた。
【０１４４】
（実施例３３）
実施例２６で作製した目付７５０ｇ／ｍ²のポリマーアロイ短繊維不織布を、３％の水酸化ナトリウム水溶液（９０℃、浴比１：５０）で２時間浸漬することにより、共重合ＰＥＴの９９％以上を除去し、Ｎ６ナノファイバー集合体からなる目付１５０および３７５ｇ／ｍ²の不織布を得た。Ｎ６ナノファイバーの数平均直径は、それぞれ６０、８６、６１および６１ｎｍであった。そして、メチルトリメトキシシランオリゴマー（ｎ＝３〜４）をイソプロピルアルコール／エチレングリコール＝１／１混合溶液に溶解し、シロキサン結合を有するシリコーンポリマーの重合触媒としてジブチルスズジアセテートをシランオリゴマーに対して４重量％加え、シリコーンポリマーのコート液を調整した。これに、Ｎ６ナノファイバー集合体からなる不織布を３０℃で２０分間で浸漬し、十分コート液を含浸させた。そして、この不織布をコート液から引き上げ、６０℃で２分間、８０℃で２分間、１００℃で２分間乾燥させるとともに、シリコーンの重合を進め、Ｎ６ナノファイバーがシリコーンポリマーでコーティングされた不織布を得た。これは優れた撥水性と難燃性を示す不織布であった。このコーティング不織布中のＮ６ナノファイバーの含有率は、８５重量％であった。
【０１４５】
（実施例３４）
実施例３３で作製したＮ６ナノファイバー集合体からなる目付１５０および３７５ｇ／ｍ²の不織布は、自重１６０％以上の含水率と自重の８０％以上の保水率を示し、吸水性と保水性に優れたものであった。ここで、含水率と保水率はサンプルを６０分間水槽に十分浸漬した後、これを引き上げ表面付着水を除去したサンプルの重量（Ａｇ）を測定し、その後これを遠心脱水機（３０００ｒｐｍで７分間）で脱水したサンプルの重量（Ｂｇ）を測定し、さらにこれを１０５℃で２時間乾燥させたサンプルの重量（Ｃｇ）を測定し、以下の式で計算した。
含水率（％）＝（Ａ−Ｃ）／Ｃ×１００（％）
保水率（％）＝（Ｂ−Ｃ）／Ｃ×１００（％）
さらに、このＮ６ナノファイバー集合体からなる不織布は、特に水を１５％以上含んだ状態では特異的な粘着性が発現した。
【０１４６】
（実施例３５）
実施例３３で作製したＮ６ナノファイバー集合体からなる不織布を用いてパップ材基布を作製した。これに薬剤を塗布したところ、薬剤の吸尽性は良好であり、しかも優れた粘着性を示し、優れたパップ材とすることができた。このパップ材中のＮ６ナノファイバーの含有率は７５重量％であった。
【０１４７】
（実施例３６）
実施例３で作製したＮ６／共重合ＰＥＴアロイ仮撚加工糸を地組織に用い、１００ｄｔｅｘ、３６フィラメントのポリブチレンテレフタレート（ＰＢＴ）糸を立毛パイル部とするトリコット編物を、２８ゲージの編機を用いて６４コースの編密度で製編し、次いで、これを３％の水酸化ナトリウム水溶液（７０℃、浴比１：１００）に１時間浸漬して、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、自動車内装用布帛を得た。この結果、得られた自動車内装用布帛の目付は１３０ｇ／ｍ²であり、Ｎ６ナノファイバーの含有率は４０重量％であった。また、Ｎ６ナノファイバー部分の目付は１２０ｇ／ｍ²であった。また、ナノファイバーの数平均による単繊維直径は８４ｎｍ（６×１０^-5ｄｔｅｘ）と従来にない細さであり、また、単繊維繊度が１×１０^-7〜１×１０^-4ｄｔｅｘの繊度比率は７８％であり、特に単繊維直径で７５〜１０４ｎｍの間に入る単繊維繊度比率は６４％であり、単繊維繊度ばらつきはごく小さいものであった。そして、これ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。
【０１４８】
（実施例３７）
実施例２で用いたＮ６／共重合ＰＥＴアロイポリマーと溶融粘度２４００ｐｏｉｓｅ（２６２℃、剪断速度１２１．６ｓｅｃ^-1）、融点２２０℃のＰＢＴを別々に溶融し、海島複合紡糸をホール数２４、吐出孔径１．０ｍｍ、吐出孔長１．０ｍｍの口金を用いて実施例２と同様に行った。このとき、海成分をアロイポリマー、島成分をＰＢＴ、島成分複合比を３５重量％、１ホールあたりの島数を３６島とした。紡出糸は９００ｍ／分で引き取り、次いで、第１ホットローラー１７の温度を８５℃、第２ホットローラー１８の温度を１３０℃、延伸倍率を３．０倍として延伸・熱処理を行い２４０ｄｔｅｘ、２４フィラメント、強度３．０ｃＮ／ｄｔｅｘ、伸度４０％、Ｕ％２．０％のポリマーアロイが海、ＰＢＴが島の海島複合糸を得た。そして、これに３００ターン／ｍの甘撚りを施した後、これを経糸および緯糸に用いて２／２のツイル織物を製織した。次いで、この織物を３％の水酸化ナトリウム水溶液（７０℃、浴比１：１００）に浸漬して、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。これにより、Ｎ６ナノファイバーとＰＢＴの重量比が５５重量％：４５重量％であるＮ６ナノファイバーとＰＢＴ超極細糸（０．０８ｄｔｅｘ）の混繊糸からなる目付２００ｇ／ｍ²の織物を得た。また、Ｎ６ナノファイバーの数平均による単繊維直径は８４ｎｍ（６×１０^-5ｄｔｅｘ）と従来にない細さであり、また、単繊維繊度が１×１０^-7〜１×１０^-4ｄｔｅｘの繊度比率は７８％であり、特に単繊維直径で７５〜１０４ｎｍの間に入る単繊維繊度比率は６４％であり、単繊維繊度ばらつきはごく小さいものであった。
【０１４９】
この織物は、Ｎ６とＰＢＴの帯電性の違いに起因した静電反発により、Ｎ６ナノファイバーが開繊し、バフィング処理やシリコーン処理無しでも超ソフトでしかも超ピーチ感があり、人肌のようなみずみずしさを持った優れた風合いを示した。さらに、ＰＢＴが織物骨格を支えるため、寸法安定性が向上するだけでなく反発感にも優れるものであった。この織物を用いてウィンドブレーカーを作製したが、Ｎ６ナノファイバーが開繊する事により優れた防風性が発現しただけでなく、超ソフトな風合いのためスポーツで激しく動いても“ガサガサ”音が無く、さらにＮ６ナノファイバーにより優れた吸湿性が発現するため着用快適性に非常に優れるものであった。また、これを家庭用洗濯機で洗濯ネットに入れずに洗濯・脱水したが、形くずれは発生せず良好な寸法安定性を示した。
【０１５０】
【発明の効果】
本発明によれば、優れた吸湿・吸着性能を持ちながら、耐久性にも優れた材料としてのナノファイバーを含む繊維構造体を得ることができる。
【０１５１】
また、本発明のナノファイバーを含む繊維構造体によって、住宅環境の改善ができるのみならず、優れた特性の産業資材や快適衣料分野等、現代社会の様々なニーズに応えることができる繊維製品や繊維利用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のナイロンナノファイバーの集合体繊維横断面を示すＴＥＭ写真である。
【図２】 実施例１のポリマーアロイ繊維の横断面を示すＴＥＭ写真である。
【図３】 実施例１のナノファイバー集合体の繊維側面の状態を示すＳＥＭ写真である。
【図４】 実施例１のナノファイバー集合体の繊維側面の状態を示す光学顕微鏡写真である。
【図５】 実施例１のナノファイバーの単糸繊度ばらつきをあらわす図である。
【図６】 実施例１のナノファイバーの単糸繊度ばらつきをあらわす図である。
【図７】 比較例４の超極細糸の単繊維繊度ばらつきをあらわす図である。
【図８】 比較例４の超極細糸の単繊維繊度ばらつきをあらわす図である。
【図９】 比較例５の超極細糸の単繊維繊度ばらつきをあらわす図である。
【図１０】 比較例５の超極細糸の繊維糸繊度ばらつきをあらわす図である。
【図１１】 紡糸機の一例を示す概略模式図である。
【図１２】 口金を示す側断面図である。
【図１３】 他の延伸機の一例を示す概略模式図である。
【図１４】 他の紡糸機の一例を示す概略模式図である。
【図１５】 他の紡糸機の一例を示す概略模式図である。
【図１６】 他の紡糸機の一例を示す概略模式図である。
【図１７】 スパンボンド紡糸装置の一例を示す概略模式図である。
【図１８】 仮撚り装置の一例を示す概略模式図である。
【符号の説明】
１：ホッパー
２：溶融部
３：スピンブロック
４：紡糸パック
５：口金
６：チムニー
７：糸条
８：集束給油ガイド
９：第１引き取りローラー
１０：第２引き取りローラー
１１：巻き取り糸
１２：計量部
１３：吐出孔長
１４：吐出孔径
１５：未延伸糸
１６：フィードローラー
１７：第１ホットローラー
１８：第２ホットローラー
１９：第３ローラー（室温）
２０：延伸糸
２１：１軸押出混練機
２２：静止混練器
２３：２軸押出混練機
２４：チップ計量装置
２５：イジェクター
２６：開繊板
２７：開繊糸条
２８：捕集装置
２９：原糸
３０：フィードローラー
３１：ヒーター
３２：冷却板
３３：回転子
３４：デリバリーローラー
３５：仮撚り加工糸[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fiber structure including nanofibers excellent in adsorption ability of water vapor and harmful substances, and a fiber (utilization) product including the fiber structure.
[0002]
[Prior art]
In recent years, housing has become highly airtight and highly insulated, and at first glance it seems that the comfort of the living environment has increased, but in fact the air permeability of the room has deteriorated and the house itself has lost its autonomous humidity control function. Therefore, various problems have occurred. Specifically, moisture tends to accumulate on the floor, ceiling, room walls, etc., mites and molds are likely to occur, and condensation is likely to occur between the room walls and the outer walls. It is a problem.
[0003]
On the other hand, traditional Japanese houses used abundant materials with autonomous humidity control functions such as wood, tatami mats, and earth walls, and so to speak, the houses breathed and adjusted the humidity. However, recently, building materials and wallpaper made of chemical products such as synthetic resins that have no humidity control function have been replaced by wood and earth walls. Also, in modern homes that have become westernized, even if wood is used as a flooring material, the surface has been coated with a non-moisture permeable material or has been chemically processed to provide a sufficient humidity control function. It was gone. Furthermore, even if we look at the interior of a room, traditional Japanese houses used plenty of processed products such as shoji, bran, and wooden furniture. It has been replaced by chemicals such as resins. For this reason, we are generally trying to adjust the temperature and humidity using an air conditioner, but in reality, there is a big difference between temperature and humidity where the air conditioner hits and where it is not, and sufficient effects cannot be obtained. In addition, there was a problem of inducing excessive cooling and heating and further worsening the living environment. In addition, due to excessive drying, viruses such as colds may increase, and static electricity may be easily generated, resulting in damage to residents' health.
[0004]
For this reason, the humidity control sheet | seat which has a humidity control layer containing the mesoporous silica which has an autonomous humidity control function on a base material is proposed. According to this, it is shown that humidity can be adjusted autonomously between 50 to 65% (refer to Patent Document 1). However, this proposal has a problem in that the humidity control layer containing mesoporous silica and the substrate are easily peeled off and the durability is poor. Furthermore, since the humidity control layer containing mesoporous silica is coated with a thickness of 80 μm, it cannot be developed in the field of textile products that require softness and texture such as clothing, curtains, carpets, bedding, and padded cotton. It was possible and there was a great limitation on application. In addition, a sheet skin material in which mesoporous silica is applied to a fabric using a polymer latex has been proposed with the aim of reducing the stuffiness between the car seat and the human body (see Patent Document 2). However, similarly to Patent Document 1, there are problems in that durability is poor due to peeling between the polymer latex layer containing mesoporous silica and the fabric, and there is a great limitation on application development due to texture hardening.
[0005]
By the way, the housing environment in recent years has a big problem of sick house syndrome in addition to the above-mentioned problem of humidity control. This is because volatile harmful substances (VOC) such as formaldehyde contained in building materials and paints gradually evaporate. However, in highly airtight houses, this VOC is not discharged outdoors and the house is filled with high concentration. The person who inhaled it complains of poor physical condition such as chemical sensitivity and dizziness. About this, although the idea of smearing diatomaceous earth etc. on the wall has been devised, such a painted wall is not compatible with recent Western-style houses, so the proportion of painted wall per unit is not enough The current situation is that the sick house syndrome has not been solved.
[0006]
For this reason, there has been a demand for a material that has excellent moisture absorption / adsorption performance, can be naturally dissolved in recent Western-style houses, and has excellent durability.
[0007]
[Patent Document 1]
JP 2000-43179 A (1-5 pages)
[0008]
[Patent Document 2]
JP-A-9-310282
[0009]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a fiber structure including nanofibers as a material that can be naturally blended into a recent Western-style house while having excellent moisture absorption / adsorption performance and also has excellent durability. Is to provide. Another object of the present invention is to provide a material that can meet various needs of modern society, such as improving the performance of comfortable clothing, industrial materials and medical materials, as well as improving the housing environment. It is in.
[0010]
[Means for Solving the Problems]
The object of the present invention is achieved by the following fiber structure. That is, the fiber structure of the present invention contains at least 10% by weight of nanofibers having the following characteristics made of an organic polymer, and the basis weight of the fibers is 20 to 2000 g / m. ² It is the fiber structure containing the nanofiber which is.
[0011]
Number average single fiber fineness = 1 × 10 ^-7 ~ 1x10 ^-Four dtex
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The fiber structure of the present invention contains nanofibers made of an organic polymer. The organic polymer in the present invention means a thermoplastic polymer typified by polyester, polyamide or polyolefin, a thermosetting polymer such as phenol resin, or a biopolymer such as DNA. From this point, a thermoplastic polymer is preferably used. Among them, many polycondensation polymers represented by polyesters and polyamides have a high melting point, and the melting point of the polymer is preferably 165 ° C. or higher because the heat resistance of the nanofiber is good. For example, polylactic acid (PLA) has a melting point of 170 ° C, polyethylene terephthalate (PET) has a temperature of 255 ° C, and nylon 6 (N6) has a temperature of 220 ° C. The polymer may contain additives such as particles, a flame retardant, or an antistatic agent. Further, other components may be copolymerized as long as the properties of the polymer are not impaired.
[0013]
The nanofiber referred to in the present invention refers to a fiber having a single fiber diameter of 1 to 250 nm, and a collection of the fibers is referred to as a nanofiber aggregate. In the present invention, the average value of the single fiber fineness in the nanofiber aggregate is important. This is done by observing the cross section of the nanofiber assembly with a transmission electron microscope (TEM) and measuring the diameter of 300 or more single fibers randomly extracted within the same cross section. And can be obtained by measuring a total of 1500 or more single fiber diameters. In these measurements, it is preferable to sample different locations from the viewpoint of ensuring the uniformity of the fiber structure or fiber product obtained from the nanofiber aggregate.
[0014]
Here, the average value (number average) of the single fiber fineness is obtained as follows. That is, the fineness is calculated from the measured single fiber diameter, and a simple average value is obtained. In the present invention, this is called “number average single fiber fineness”. In the present invention, the number average single fiber fineness is 1 × 10. ^-7 ~ 1x10 ^-Four It is important to be dtex (corresponding to 1 to 100 nm in terms of single fiber diameter). This is a fineness of about 1 / 1,000,000 compared to ordinary fibers, and a fineness of 1/1000 to 1/10000 compared to conventional ultra-thin yarns by sea-island composite spinning. It can be set as the cloth for clothes and the cloth for interiors which have the completely different texture from a super fine thread. The number average single fiber fineness is preferably 1 × 10 ^-Five ~ 6 × 10 ^-Five dtex (corresponding to 40 to 80 nm in terms of single fiber diameter).
[0015]
Moreover, the single fiber fineness variation of a nanofiber is evaluated as follows. That is, the single fiber fineness of each nanofiber is set to dt. _i And the sum of the total fineness (dt ₁ + Dt ₂ + ... + dt _n ). The frequency (number) of nanofibers having the same single fiber fineness is counted, and the product divided by the total fineness is defined as the fineness ratio of the single fiber fineness. This corresponds to the weight fraction (volume fraction) of each single fiber fineness component with respect to the whole (nanofiber aggregate), and the single fiber fineness component having a large value contributes greatly to the properties of the nanofiber aggregate. In the present invention, 60% or more of the fineness ratio is 1 × 10 ^-7 ~ 1x10 ^-Four It is preferably in the range of dtex (corresponding to 1 to 100 nm in terms of single fiber diameter). That is, 1 × 10 ^-Four This means that the presence of nanofibers larger than dtex (corresponding to a single fiber diameter of 100 nm) is close to zero. As a result, the function of the nanofiber can be fully exhibited and the product quality stability can also be improved. For example, when used in a surface polishing cloth for hard disks, which is a kind of industrial material, the fineness varies. Therefore, even nanofibers can uniformly carry abrasive grains, and as a result, the smoothness of the hard disk surface can be dramatically improved. Furthermore, when the surface of the fiber structure is covered with nanofibers that are much thinner than before, the barrier property of gas or liquid may be increased. More preferably, 60% or more of the fineness ratio is 1 × 10 ^-7 ~ 6 × 10 ^-Five It is a range of dtex (corresponding to 1 to 80 nm in terms of single fiber diameter). More preferably, 75% or more of the fineness ratio is 1 × 10 ^-7 ~ 6 × 10 ^-Five It is a range of dtex (corresponding to 1 to 80 nm in terms of single fiber diameter).
[0016]
Another index of variation in fineness is the fineness ratio of single fibers in which the single fiber diameter difference is in the range of 30 nm. This means the concentration of variation near the central fineness. The higher the ratio, the smaller the variation. In the present invention, the fineness ratio of the fiber yarn having a single fiber diameter difference of 30 nm is preferably 50% or more. More preferably, it is 70% or more.
[0017]
In the present invention, the nanofiber aggregate is preferably in the form of long fibers and / or spun yarn. Here, the long fiber and / or spun yarn shape refers to the following state. That is, it means a state in which an assembly in which nanofibers are oriented one-dimensionally is continuous with a finite length. The length of the long fiber and / or spun yarn-shaped nanofiber assembly of the present invention is preferably several meters or more as in the case of ordinary long fibers and spun yarn. Thereby, it can be set as various fiber products, such as a short fiber, a nonwoven fabric, or a heat compression molding object as well as a textile fabric and a knitted fabric.
[0018]
Further, the nanofiber of the present invention has a feature that the specific surface area is remarkably increased because the single fiber diameter is much thinner than that of the conventional fiber. For this reason, the characteristic characteristic of the nanofiber which was not seen with the normal fiber as follows is shown.
[0019]
For example, a significant improvement in adsorption characteristics can be mentioned. Actually, the adsorption of water vapor, i.e., the hygroscopic performance, is equivalent to the single fiber fineness of 10 ^-Five Detx level polyamide nanofiber aggregate and single fiber fineness 10 ^-2 When compared with ordinary polyamide superfine yarn of dtex level, the hygroscopicity of the polyamide nanofiber aggregate of the present invention may reach 6% compared to the hygroscopicity of the normal polyamide superfine yarn of about 2%. It was. This hygroscopic performance is a very important characteristic not only in terms of humidity control in a residential environment but also in comfortable / high-end clothing, and is preferably 4% or more in the present invention. The Journal of Textile Society, vol. 57, 69 (2001). Describes that the contribution of moisture absorption of nylon fiber is about 1/1000 of the amount of moisture absorption of the entire fiber, and the specific surface area is dramatically increased as compared with the conventional nanofiber of the present invention. In this way, it is possible to draw out adsorption performance that has not been conceived in the past.
[0020]
In addition, although the desorption performance of the adsorbed substance is important, in the nanofiber of the present invention, the adsorbed molecules are only loosely bound to the nanofiber surface, and can be easily desorbed with a dryer or sun-dried, It can be reused as an adsorbing material.
[0021]
Furthermore, in the nanofiber aggregate of the present invention, a large number of gaps of several nanometers to 100 nm are created between the nanofibers, so that the adsorbed molecules can freely enter and exit, and the adsorption / desorption is facilitated.
[0022]
In addition, the fiber structure containing the nanofiber of the present invention can contain an adsorbent as necessary. This is effective when a harmful substance is selectively adsorbed. For example, when an acidic substance such as a metal halide is used as the adsorbent, the adsorption efficiency of a basic substance such as trimethylamine is improved. On the other hand, when a basic substance such as polyamine is used, the adsorption efficiency of acidic substances such as isovaleric acid and aldehyde gases is improved.
[0023]
In addition, when the nanofiber aggregate of the present invention is used for clothing, it is possible to obtain a fiber product having an excellent texture with a squeaky feeling like silk and a dry feeling like rayon. Furthermore, by opening the nanofibers from the nanofiber assembly by buffing treatment or chemical treatment with silicone, etc., an excellent texture of super peach feeling and a moist touch like human skin, which was not previously thought of Can also be obtained.
[0024]
The fiber structure referred to in the present invention refers to a general one-dimensional, two-dimensional or three-dimensional structure mainly composed of fibers, but examples of one-dimensional include long fibers, short fibers, spun yarn, rods, etc. Two-dimensional examples include fabrics and sheets such as woven and knitted fabrics and nonwoven fabrics, and three-dimensional examples include fabric modules and braids, thermoformed bodies, and cotton. In the present invention, clothing, curtains, car seats, carpets and the like made of this fiber structure are called fiber products. Moreover, in this invention, what combined this fiber structure and other materials, such as a film and a cylinder, is called the fiber utilization product using a fiber structure. Examples of this include air purifiers, water purifiers, building materials, cell adsorption columns and automobile parts.
[0025]
The fiber structure of the present invention can express various functions and textures that have not been conceived by the nanofiber as described above. However, in order to fully exhibit the characteristics of the nanofiber, the entire fiber structure In contrast, it is important to contain 10% by weight or more of nanofibers. The optimum value of the nanofiber content varies depending on the type of the fiber product, but it is preferably 50% by weight or more in order to fully express the moisture absorption / adsorption function.
[0026]
The fiber basis weight of the fiber structure of the present invention is 20 to 2000 g / m. ² Is important. Here, the fiber basis weight is a value obtained by dividing the fiber weight by the area of the fiber part. The smaller the basis weight, the lighter the weight, but the structure becomes loose and the dimensional stability and durability are inferior. Firmly improve dimensional stability and durability. In particular, in the present invention, the use of nanofibers tends to deteriorate the dimensional stability and durability, so the basis weight is 20 g / m. ² As described above, it is particularly important to ensure dimensional stability and durability. In addition, the basis weight is 2000 g / m. ² A certain amount of lightness can be secured by the following. The optimum weight per unit area varies depending on the type of fiber product, but it is 25-40 g / m for non-woven fabrics for packaging. ² Light and moderate, 50-200 g / m for clothing ² About 100 to 250 g / m for curtains ² About 100 to 350 g / m for car seats ² In the case of heavy goods such as carpet, 1000-1500 g / m ² It is preferable to set the degree. Especially for products that require washing, 50 g / m to prevent deformation during washing. ² The above is preferable.
[0027]
Moreover, in order to improve the dimensional stability, the nanofiber of the present invention may be enclosed in an organic capsule or mixed with other fibers. When hollow fibers are used as the organic capsule, the nanofibers are contained in the hollow portion, so that the dimensional stability and the handleability of the product are greatly improved while maintaining the adsorption performance. In addition, when nanofibers are mixed with other fibers, in addition to methods for clothing such as mixed fiber, union and union, non-woven methods such as bonding of fabrics and other substrates (films / films) For example, a method of fixing with a plate, a bar, or the like can also be used.
[0028]
Although the manufacturing method of the nanofiber aggregate of the present invention is not particularly limited, for example, the following method can be employed.
[0029]
That is, a polymer alloy melt obtained by alloying two or more kinds of polymers having different solubility in a solvent is formed, and after spinning, it is solidified by cooling and fiberized. Then, stretching and heat treatment are performed as necessary to obtain polymer alloy fibers. And the nanofiber aggregate of the present invention can be obtained by dissolving and removing the easily soluble polymer with the solvent.
[0030]
Here, it is important to control the island size by making the easily soluble polymer into the sea (matrix) and the hardly soluble polymer into the island (domain) in the polymer alloy fiber that is the precursor of the nanofiber assembly. . Here, the island size is obtained by observing the cross section of the polymer alloy fiber with a transmission electron microscope (TEM) and evaluating it in terms of diameter. Since the diameter of the nanofiber is almost determined by the island size in the precursor, the distribution of the island size is designed according to the diameter distribution of the nanofiber of the present invention. For this reason, kneading of the polymer to be alloyed is very important, and in the present invention, high kneading is preferably performed by a kneading extruder, a stationary kneader or the like. In addition, since kneading is insufficient with simple chip blending, it is difficult to disperse islands with a size of several tens of nm as in the present invention.
[0031]
Specific guidelines for kneading depend on the polymer to be combined, but when using a kneading extruder, it is preferable to use a twin-screw extrusion kneader, and when using a static kneader, splitting is preferred. The number is preferably 1 million or more.
[0032]
In addition, a combination of polymers is also important for ultra-fine dispersion of islands with a size of several tens of nanometers.
[0033]
In order to make the island domain (cross section of the nanofiber) close to a circle, the island polymer and the sea polymer are preferably incompatible. However, it is difficult for the island polymer to be sufficiently finely dispersed by a simple combination of incompatible polymers. For this reason, it is preferable to optimize the compatibility of the polymer to be combined, but one index for this purpose is the solubility parameter (SP value). What is SP value (evaporation energy / molar volume) ^1/2 It is a parameter that reflects the cohesive strength of the substance defined by the above, and there is a possibility that a polymer alloy having good compatibility can be obtained between materials having close SP values. The SP value is known for various polymers, and is described, for example, in “Plastic Data Book”, edited by Asahi Kasei Amidus Co., Ltd./Plastics Editorial Department, page 189. The difference in SP value between the two polymers is 1-9 (MJ / m ^Three ) ^1/2 When it is, it is easy to make both the island domain circularization and ultrafine dispersion by incompatibility easy, and is preferable. For example, the difference in SP value between N6 and PET is 6 (MJ / m ^Three ) ^1/2 However, N6 and polyethylene (PE) have a difference in SP value of 11 (MJ / m ^Three ) ^1/2 This is an unfavorable example.
[0034]
When the difference in melting point between polymers is 20 ° C. or less, it is easy to knead highly efficiently because it is difficult to cause a difference in the melting state in the extrusion kneader, particularly when kneading using an extrusion kneader. In addition, when a polymer which is easily decomposed or thermally deteriorated is used as one component, it is necessary to keep the kneading and spinning temperature low, which is also advantageous. Here, when the polymer is an amorphous polymer, since there is no melting point, it is replaced with a glass transition temperature, a heat distortion temperature, or a Vicat softening temperature.
[0035]
Furthermore, the melt viscosity is also important. If the melt viscosity of the polymer that forms the island is set low, the island polymer is likely to be deformed by shearing force. Is a preferred embodiment. However, if the island polymer is excessively low in viscosity, it tends to be seamed and the blend ratio with respect to the whole fiber cannot be increased. Therefore, the island polymer viscosity is preferably 1/10 or more of the sea polymer viscosity.
[0036]
In addition, the blend ratio of the island polymer is important from the viewpoint of increasing the fabric weight of the fiber structure. For example, if the blend ratio of the island polymer is 10% by weight and the remaining 90% by weight of the sea polymer is removed, the basis weight of the fiber structure becomes about 1/10 of the initial, so the fiber structure is loose. It becomes a structure and the dimensional stability is greatly reduced. In order to improve the dimensional stability of the fiber structure, the blend ratio of the island polymer is preferably 20% by weight or more, more preferably 40% by weight or more based on the entire polymer alloy fiber. However, when the blend ratio of the island polymer is increased, it is difficult to form an island. Therefore, the blend ratio of the island polymer is preferably 60% by weight or less, although it depends on the melt viscosity balance with the sea polymer.
[0037]
In the polymer alloy, since the island polymer and the sea polymer are incompatible with each other, the island polymers are more stably aggregated to be thermodynamically stable. However, in order to forcibly disperse the island polymer by ultra-fine dispersion, this polymer alloy has a much more unstable polymer interface than a normal polymer blend having a large dispersion diameter. For this reason, when this polymer alloy is simply spun, there are many unstable polymer interfaces, so the “ballus phenomenon” occurs where the polymer flow swells immediately after the polymer is discharged from the die, or the surface of the polymer alloy becomes unstable. As a result, the yarn may become unsatisfactory, resulting in an excessively large and uneven thread, and the spinning itself may become impossible (a negative effect of the ultrafine dispersion polymer alloy). In order to avoid such a problem, it is preferable to reduce the shear stress between the base hole wall and the polymer when discharging from the base. Here, the shear stress between the base hole wall and the polymer is the Hagen Poisyu equation (shear stress (dyne / cm ² ) = R × P / 2L). Where R: radius of the nozzle discharge hole (cm), P: pressure loss at the nozzle discharge hole (dyne / cm) ² ), L: Base discharge hole length (cm). P = (8LηQ / πR ^Four ): Η: polymer viscosity (poise), Q: discharge amount (cm ^Three / Sec), π: pi. 1 dyne / cm of CGS unit system ² Is 0.1 Pa in the SI unit system.
[0038]
For example, in ordinary polyester melt spinning, the shear stress between the hole wall of the die and the polymer is 1 MPa or more, but when melt spinning the polymer alloy as in the present invention, it is preferably 0.3 MPa or less. . For this purpose, the diameter of the die hole is large and the length of the die hole tends to be shortened. However, if this is done excessively, the meterability of the polymer in the die hole will be reduced, resulting in fineness spots and poor spinnability. For this reason, it is preferable to use a die having a polymer measuring part above the discharge hole. Specifically, it is preferable that the polymer metering section is a portion whose hole diameter is narrowed from the discharge hole.
[0039]
Further, from the viewpoint of sufficiently ensuring spinnability and spinning stability in melt spinning, the die surface temperature is preferably 25 ° C. or higher from the melting point of the sea polymer.
[0040]
As described above, when spinning the ultrafinely dispersed polymer alloy used in the present invention, the spinneret design is important, but the cooling condition of the yarn is also important. As described above, since the polymer alloy is a very unstable molten fluid, it is preferable to quickly cool and solidify after discharging from the die. For this reason, it is preferable that the distance from a nozzle | cap | die to the cooling start shall be 1-15 cm. Here, the start of cooling means a position where positive cooling of the yarn is started, but in the actual melt spinning apparatus, it is replaced with this at the upper end of the chimney.
[0041]
The spinning speed is not particularly limited, but high speed spinning is more preferable from the viewpoint of increasing the draft in the spinning process. The spinning draft is preferably 100 or more from the viewpoint of reducing the diameter of the obtained nanofiber.
[0042]
The spun polymer alloy fibers are preferably subjected to stretching and heat treatment. The preheating temperature during stretching is the glass transition temperature (T _g ) By setting the temperature above, the yarn unevenness can be reduced.
[0043]
In this nanofiber assembly manufacturing method, the combination of polymers as described above, spinning and stretching conditions are optimized, so that the island polymer is ultrafinely dispersed to several tens of nanometers, and the polymer alloy fibers with small thread irregularities are formed. It is possible to get. In this way, by using polymer alloy fibers with small thread irregularities in the longitudinal direction of the yarn as a precursor, it is possible to obtain a nanofiber aggregate with small single fiber fineness variation not only in a certain section but also in any section in the longitudinal direction. is there. It is preferable that the Worcester plaque of the polymer alloy fiber which is a precursor is 15% or less, more preferably 5% or less.
[0044]
The nanofiber aggregate is obtained by eluting the readily soluble polymer, which is a sea polymer, from the polymer alloy fiber thus obtained with a solvent. In this case, an aqueous solvent may be used as the solvent. It is preferable from the viewpoint of reducing the environmental load. Specifically, it is preferable to use an alkaline aqueous solution or hot water. For this reason, as the easily soluble polymer, a polymer that is hydrolyzed by alkali such as polyester, or a hot water-soluble polymer such as polyalkylene glycol, polyvinyl alcohol, or a derivative thereof is preferably used.
[0045]
By such a production method, a nanofiber aggregate in the form of a spun yarn in which nanofibers having a fiber length of several tens of μm or more in some cases are in some cases bonded or entangled can be obtained. Further, in the above production method, particularly when a stationary kneader is positioned directly above the die, a nanofiber aggregate having a long fiber shape in which nanofibers are theoretically extended infinitely may be obtained.
[0046]
In the present invention, unlike conventional nanofibers, nanofibers can be stretched and heat-treated for the first time by stretching and heat-treating polymer alloy fibers, which are precursors. Can now be controlled. Here, the strength of the nanofiber aggregate of the present invention is preferably 1 cN / dtex or more because the mechanical properties of the fiber product can be improved. The strength of the nanofiber aggregate is more preferably 2 cN / dtex or more. It is also possible to crimp the polymer alloy fiber as a precursor.
[0047]
The fiber structure containing the nanofiber of the present invention is not limited to fabrics such as woven and knitted fabrics and non-woven fabrics, and can take various fiber product forms such as thermoformed products. A wide range of applications such as bonding to other materials is possible. In order to improve the housing environment, it can be used for interior products such as curtains, wallpaper, carpets, mats, and furniture, and can also be used for chemical filters for removing chemical contaminants for clean rooms. Further, it can be used as a deodorant sheet in a toilet or a room, a vehicle interior material for improving a vehicle interior environment, more specifically, as a seat upholstery or a ceiling skin material. Furthermore, it can be used for clothing having comfortable and deodorizing performance, more specifically, for clothing materials such as inners, shirts, blousons, pants, coats, artificial leather, cups and pads. Furthermore, it can be suitably used for industrial materials such as wiping cloths, polishing cloths and filters, and medical uses such as cell adsorbents.
[0048]
【Example】
Hereinafter, the fiber structure containing the nanofiber of the present invention will be described in detail using examples. In addition, the following methods were used for the measuring method of the characteristic etc. in an Example.
[0049]
A. Polymer melt viscosity
The polymer melt viscosity was measured with a Capillograph 1B manufactured by Toyo Seiki. The polymer storage time from sample introduction to measurement start was 10 minutes.
[0050]
B. Melting point
Using Perkin Elmaer DSC-7, the peak top temperature indicating the melting of the polymer at 2nd run was taken as the melting point of the polymer. At this time, the rate of temperature increase was 16 ° C./min, and the sample amount was 10 mg.
[0051]
C. Shear stress at the nozzle discharge hole
The shear stress between the base wall and the polymer is expressed by the Hagen Poisyu equation (shear stress (dyne / cm ² ) = R × P / 2L). Here, R: radius of the nozzle discharge hole (cm), P: pressure loss at the nozzle discharge hole (dyne / cm) ² ), L: Base discharge hole length (cm). Also, P = (8LηQ / πR ^Four ): Η: polymer viscosity (poise), Q: discharge amount (cm ^Three / Sec), π: pi. Here, as the polymer viscosity, a value at the temperature and shear rate of the die discharge hole was used. When the kneaded portion was incorporated into the spinning process, the discharged polymer alloy was rapidly cooled at 5 cm below the die, the gut was sampled, and after cutting this, it was dried again and the viscosity of the polymer alloy was measured with a capillograph.
[0052]
D. Worcester spots of polymer alloy fibers (U%)
Measurement was performed in the normal mode at a yarn feeding speed of 200 m / min using a USTER TESTER 4 manufactured by Zerbegger Worcester.
[0053]
E. Fiber cross-sectional observation by TEM
An ultrathin section was cut in the cross-sectional direction of the fiber, and the fiber cross-section was observed with a transmission electron microscope (TEM). Nylon was metal dyed with phosphotungstic acid.
TEM apparatus: H-7100FA type manufactured by Hitachi.
[0054]
F. Single fiber fineness and diameter by number average of nanofibers
The average value of the single fiber fineness is obtained as follows. That is, the fiber cross-sectional photograph by TEM was used to calculate the single fiber diameter and fineness using image processing software (WINROOF), and a simple average value was obtained. This was defined as “number average single fiber fineness”. At this time, the number of nanofibers used for the average was measured on the diameter of 300 or more single fibers randomly selected in the same cross section, but sampling was performed at 5 locations and calculated using a total diameter of 1500 or more single fibers. did.
[0055]
G. Single fiber fineness variation of nanofiber
The single fiber fineness variation of the nanofiber is evaluated as follows. That is, using the data used when determining the single fiber fineness by the above number average, the single fiber fineness of each nanofiber is expressed as dt. _i And the sum of the total fineness (dt ₁ + Dt ₂ + ... + dt _n ). The frequency (number) of nanofibers having the same single fiber fineness is counted, and the product divided by the total fineness is defined as the fineness ratio of the single fiber fineness.
[0056]
H. Diameter variation width of nanofiber
The diameter variation width of the nanofiber is evaluated as follows. That is, the evaluation is performed based on the fineness ratio of single fibers in which the single fiber diameter difference falls within the width of 30 nm near the center value of the single fiber diameter of the nanofiber. This means the degree of concentration of variation around the central fineness, and the higher the fineness ratio, the smaller the variation. The data used when obtaining the single fiber fineness by the above number average was also used.
[0057]
I. SEM observation
A platinum-palladium alloy was deposited on the fiber, and the fiber side surface was observed with a scanning electron microscope.
SEM apparatus: Hitachi S-4000 type.
[0058]
J. et al. Mechanical properties
The weight of the nanofiber aggregate 10m was measured n = 5 times, and the fineness (dtex) of the nanofiber aggregate was determined from the average value. Then, at room temperature (25 ° C.), an initial sample length = 200 mm, a pulling rate = 200 mm / min, and a load-elongation curve was obtained under the conditions shown in JIS L1013. Next, the load value at the time of breaking was divided by the initial fineness, which was used as the strength, and the elongation at break was divided by the initial sample length to obtain a strength / elongation curve.
[0059]
K. Hygroscopicity (ΔMR)
The sample is weighed in a weighing bottle of about 1 to 2 g, dried at 110 ° C. for 2 hours, dried, and weighed (W0). (W65). And this is hold | maintained at 30 degreeC and relative humidity 90% for 24 hours, Then, a weight is measured (W90). The calculation is performed according to the following formula.
MR65 = [(W65−W0) / W0] × 100% (1)
MR90 = [(W90−W0) / W0] × 100% (2)
ΔMR = MR90−MR65 (3).
[0060]
L. Removal test for harmful and offensive odor gas
After fixing 3.0 g of a sample in a 500 ml polyethylene container, a malodorous substance was introduced into the container. And after sealing, the container was hold | maintained at 50 degreeC for 1 minute, and the malodorous substance was fully vaporized. And after leaving for a predetermined time at 30 degreeC, the air in a container was sampled and the malodorous substance density | concentration was measured with the gas detection tube made from Gastec Corporation.
[0061]
Example 1
Melt viscosity 530 poise (262 ° C., shear rate 121.6 sec ^-1 ), N6 (20 wt%) with a melting point of 220 ° C. and a melt viscosity of 3100 poise (262 ° C., shear rate of 121.6 sec) ^-1 ) Copolymerized PET (80 wt%) having a melting point of 225 ° C. and 8 mol% of isophthalic acid having a melting point of 225 ° C. and 4 mol% of bisphenol A was kneaded at 260 ° C. with a twin-screw extruder kneader to obtain a polymer alloy chip. Obtained. This polymer alloy chip was melted from the hopper 1 at the melting part 2 at 275 ° C. and led to the spin block 3 at a spinning temperature of 280 ° C. The polymer alloy melt was filtered with a metal nonwoven fabric having a limit filtration diameter of 15 μm, and then melt-spun from the base 5 of the spin pack 4 with a base surface temperature of 262 ° C. (see FIG. 11). At this time, as shown in FIG. 12, a die having a measuring portion 12 having a diameter of 0.3 mm at the upper portion of the discharge hole and having a discharge hole diameter 14 of 0.7 mm and a discharge hole length 13 of 1.75 mm was used. And the discharge amount per single hole at this time was 1.0 g / min. At this time, the shear stress between the base hole wall and the polymer was 0.058 MPa (the viscosity of the polymer alloy was 1400 poise, 262 ° C., shear rate 416 sec. ^-1 ) And low enough. Further, in FIG. 11, the distance from the lower surface of the base to the cooling start point (the upper end of the chimney 6) was 9 cm. The discharged yarn 7 is cooled and solidified over 1 m with a cooling air of 20 ° C., and is fed by a focused oiling guide 8 installed 1.8 m below the base 5, and then the unheated first take-up roller 9 and second 11 windings were taken up as a take-up yarn at 900 m / min through the take-up roller 10. The spinnability at this time was good, and there was no yarn breakage during continuous spinning for 24 hours. Then, the obtained unstretched 15 is fed by a feed roller 16, and the first hot roller 17 is set to 90 ° C., the second hot roller 18 is set to 130 ° C., and the third roller 19 (room temperature) is stretched and heat treated. The drawn yarn 20 was obtained (see FIG. 13). At this time, the draw ratio between the first hot roller 17 and the second hot roller 18 was set to 3.2 times. The obtained polymer alloy fiber exhibited excellent properties of 120 dtex, 36 filaments, strength 4.0 cN / dtex, elongation 35%, U% = 1.7%. Moreover, when the cross section of the obtained polymer alloy fiber was observed with TEM, copolymerized PET showed the sea (thin part), N6 (dense part) showed the island-island structure (see FIG. 2), and the island N6. The number average diameter was 53 nm, and a polymer alloy fiber in which N6 was ultrafinely dispersed was obtained.
[0062]
Three polymer alloy fibers obtained here were mixed together to produce a knitted fabric by circular knitting, and this was immersed in a 3% aqueous sodium hydroxide solution (90 ° C., bath ratio 1: 100) for 2 hours, 99% or more of the copolymerized PET in the polymer alloy fiber was hydrolyzed and removed. As a result, the weight of the obtained circular knitted fabric made of N6 single yarn is 60 g / m. ² Met. In this circular knitted fabric, even though the copolymerized PET, which is a sea polymer, was removed, it was continuous like a long fiber or a spun yarn when viewed macroscopically, and maintained a circular knitted fabric shape. And this circular knitted fabric is completely different from the circular knitted fabric made of normal N6 fiber, and there is no “smoothness” peculiar to nylon, conversely, “squeezed feeling” like silk and “dry feeling” like rayon. The knitted fabric with
[0063]
The yarn was pulled out from this circular knitted fabric made of N6 nanofibers, and the fiber side surface was first observed with an optical microscope. The fiber diameter was about 2/3 of the fiber before alkali treatment, and the sea polymer was removed. It was found that the shrinkage occurred in the fiber radial direction (see FIG. 4). Next, when the side surface of the fiber was observed by SEM, it was found that this yarn was not a single yarn but a nanofiber aggregate in which numerous nanofibers were joined together in some places (see FIG. 3). . Moreover, the space | interval of the nanofibers of this N6 nanofiber aggregate is about 1 to several hundreds nm, and extremely fine voids existed. Further, the result of observing the cross section of the fiber by TEM is shown in FIG. 1, and it was found that the N6 nanofiber has a single fiber diameter of about several tens of nanometers. The single fiber diameter based on the number average of the nanofibers is 56 nm (3 × 10 ^-Five dtex), which is a fineness not found in the past. The single fiber fineness is 1 × 10 ^-7 ~ 9x10 ^-Five The fineness ratio of dtex (1-100 nm in terms of single fiber diameter) is 99%, in particular, the single fiber fineness ratio that falls between 55-84 nm in terms of single fiber diameter is 71%, and the single fiber fineness variation is very small. there were. The single fiber diameter and single fiber fineness histograms analyzed from the TEM photographs are shown in FIGS. 5 and 6. At this time, the number (frequency) and fineness ratio of the single fiber diameter were counted in increments of 10 nm. The single fiber diameter in increments of 10 nm means that, for example, a single fiber diameter of 55 to 64 nm was counted as a single fiber diameter of 60 nm, and a single fiber diameter of 75 to 84 nm was counted as a single fiber diameter of 80 nm.
[0064]
Further, when the moisture absorption rate (ΔMR) of the circular knitted fabric made of this N6 nanofiber was measured, it showed an excellent moisture absorption of 6%, surpassing that of cotton. Further, when the mechanical properties of the yarn comprising this N6 nanofiber aggregate were measured, the strength was 2.0 cN / dtex and the elongation was 50%.
[0065]
Furthermore, when buffing was performed on this circular knitted fabric, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin. Further, the circular knitted fabric without buffing is immersed in a 10 wt% aqueous solution of Silcote PP (specially modified silicone / trade name, manufactured by Matsumoto Yushi Co., Ltd.), and the processing liquid is circular knitted so that the pickup rate of the aqueous solution is 150%. Granted to the ground. After applying the treatment liquid, it was dried in an oven at 110 ° C. for 3 minutes in a relaxed state. After drying, the cloth was treated and showed a delicate touch different from buffing and a moist and fresh texture like human skin. Further, there was a feeling of cool contact. In addition, these circular knitted fabrics were put into a washing net by a household washing machine and washed and dehydrated. However, they did not lose shape and showed good dimensional stability.
[0066]
(Example 2)
Melt viscosity 5000 poise (262 ° C., shear rate 121.6 sec ^-1 ), Melt spinning was performed in the same manner as in Example 1 using a blending ratio of N6 having a melting point of 220 ° C. of 50% by weight with respect to the whole polymer alloy and a 36-hole die. At this time, the shear stress between the die hole wall and the polymer was 0.15 MPa. The spinnability at this time was good, and there was no yarn breakage during continuous spinning for 24 hours. This was then stretched and heat-treated in the same manner as in Example 1 to obtain a polymer alloy fiber having excellent characteristics of 128 dtex, 36 filament, strength 4.3 cN / dtex, elongation 37%, U% = 2.5%. It was. When the cross section of the obtained polymer alloy fiber was observed with a TEM, as in Example 1, copolymer PET was the sea, N6 was the island-island structure, and the number average diameter of the island N6 was 80 nm. An ultrafinely dispersed polymer alloy fiber was obtained.
[0067]
Two polymer alloy fibers obtained here were combined, and in the same manner as in Example 1, a basis weight of 150 g / m consisting of an aggregate of spun yarn-shaped N6 nanofibers was obtained by alkali treatment. ² I got a circular knitted fabric. Furthermore, as a result of analyzing the single fiber fineness variation of these nanofibers in the same manner as in Example 1, the single fiber diameter based on the number average of the nanofibers was 84 nm (6 × 10 6 ^-Five dtex), which is a fineness not found in the past. The single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. Further, the yarn comprising this N6 nanofiber aggregate had a strength of 2.6 cN / dtex and an elongation of 50%.
[0068]
Further, this circular knitted fabric was dipped in a 10 wt% aqueous solution of Silcote PP (specially modified silicone / trade name, manufactured by Matsumoto Yushi Co., Ltd.), and the treatment liquid was applied to the circular knitted fabric so that the pickup rate of the aqueous solution was 150%. . After applying the treatment liquid, it was dried in an oven at 110 ° C. for 3 minutes in a relaxed state. After drying, the cloth was treated and showed a delicate touch different from buffing and a moist and fresh texture like human skin. Further, there was a feeling of cool contact. Moreover, this circular knitted fabric was put into a washing net with a household washing machine and washed and dehydrated. However, it did not lose its shape and showed good dimensional stability.
[0069]
(Example 3)
The polymer alloy fiber produced in Example 2 was subjected to false twisting using the apparatus shown in FIG. Specifically, polymer alloy fiber raw yarn 29 is supplied by a feed roller 30, heated by a heater 31, cooled by a cooling plate 32, and twisted by a rotor 33 to form a false twisted yarn 35. At this time, a spindle was used as the rotor 33, the temperature of the heater 31 was 180 ° C., and the draw ratio, which is the difference in peripheral speed between the feed roller 30 and the delivery roller 34, was 1.01. Here, using the obtained false twisted yarn 35, the basis weight of 100 g / m consisting of a nanofiber aggregate in the form of spun yarn by alkali treatment was used in the same manner as in Example 1. ² I got a circular knitted fabric. Furthermore, as a result of analyzing the single fiber fineness variation of these nanofibers in the same manner as in Example 1, the single fiber diameter based on the number average of the nanofibers was 84 nm (6 × 10 6 ^-Five dtex) and unprecedented fineness, and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. Moreover, this N6 nanofiber false twisted yarn had a strength of 2.0 cN / dtex and an elongation of 45%.
[0070]
Further, when this circular knitted fabric was treated with silicone in the same manner as in Example 2, it showed a delicate touch and a moist and fresh texture like human skin. Further, there was a feeling of cool contact. This circular knitted fabric was put into a washing net with a household washing machine and washed and dehydrated, but it did not lose its shape and showed good dimensional stability.
[0071]
Example 4
The polymer alloy false twisted yarn produced in Example 3 was subjected to a sweet turn of 300 turns / m, and a 2/2 twill woven fabric was produced using an S twist / Z twist double yarn. As in Example 1, the basis weight is 150 g / m consisting of a spun yarn-shaped nanofiber assembly by alkali treatment. ² Of twill. Furthermore, as a result of analyzing the single fiber fineness variation of these nanofibers in the same manner as in Example 1, the single fiber diameter based on the number average of the nanofibers was 84 nm (6 × 10 6 ^-Five dtex) and unprecedented fineness, and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. Moreover, this N6 nanofiber false twisted yarn had a strength of 2.0 cN / dtex and an elongation of 45%.
[0072]
Further, when this 2/2 twill fabric was subjected to silicone treatment in the same manner as in Example 2, it showed a delicate touch and a moist and fresh texture like human skin. Further, there was a feeling of cool contact. Further, this 2/2 twill fabric was put in a washing net by a household washing machine and washed and dehydrated. However, the shape did not deform and showed good dimensional stability.
[0073]
(Comparative Example 1)
Melt viscosity 1800 poise (290 ° C., shear rate 121.6 sec ^-1 ), With a melting point of 255 ° C PET as an island component, a melt viscosity of 1000 poise (290 ° C, shear rate of 121.6 sec) ^-1 ), Using a polystyrene (PS) having a Vicat softening temperature of 107 ° C. as a sea component, a sea-island composite yarn was obtained according to the description in Example 1 of JP-A-53-106872. Then, as described in Examples in JP-A-53-106872, PS was removed by 99% or more by trichlorethylene treatment to obtain a super fine yarn. When the fiber cross section of the obtained ultrafine yarn was observed by TEM, the single fiber diameter of the ultrafine yarn was as large as 2.0 μm (0.04 dtex). The hygroscopic property of the circular knitted fabric using this super extra fine yarn was as low as 0.1%. In addition, an ammonia deodorization test was performed as a test for removing harmful and offensive odorous substances. However, the deodorization test was performed only up to 180 ppm in 10 minutes against the initial concentration of 200 ppm, and there was almost no deodorizing ability.
[0074]
(Comparative Example 2)
Melt viscosity 500 poise (280 ° C, 121.6 sec ^-1 ), N6 with a melting point of 220 ° C. and a melt viscosity of 2100 poise (280 ° C., 121.6 sec) ^-1 ) PET having a melting point of 255 ° C. was chip-blended so that the N6 blend ratio was 20% by weight, and then melted at 290 ° C., the spinning temperature was 296 ° C., the die surface temperature was 280 ° C., the number of die holes was 36, and the discharge hole diameter was 0. .30mm, discharge hole length Melt spinning was carried out in the same manner as in Example 1 using a 50 mm barrel cap, and the undrawn yarn was wound up at a spinning speed of 1000 m / min. However, it is a simple chip blend, and since the melting point difference between the polymers is large, the blend spots of N6 and PET are large, and not only a large ball is generated under the base, but also the stringiness is poor, and the yarn is stable. Although it could not be wound up, a small amount of unstretched yarn was obtained, and the first hot roller 17 was stretched in the same manner as in Example 1 at a temperature of 85 ° C. and a stretch ratio of 3 times to stretch 100 dtex and 36 filaments. I got a thread.
[0075]
Using this drawn yarn, a circular knitted fabric was formed in the same manner as in Example 1, and 99% or more of the PET component was removed by alkali treatment. N6 single yarn was pulled out from the obtained circular knitted fabric, and the cross section of the fiber was observed with TEM. The single fiber diameter was 400 nm to 4 μm (single fiber fineness 1 × 10 ^-3 ~ 1x10 ^-1 dtex) was confirmed to be produced. However, the single fiber fineness based on the number average is 9 × 10. ^-3 It was as large as dtex (single fiber diameter: 1.0 μm). Further, the single fiber fineness variation of the N6 ultrafine yarn was also large. The hygroscopicity of the circular knitted fabric using this super extra fine yarn was as low as 2%. Further, ammonia was deodorized as a test for removing harmful and offensive odorous substances. However, the deodorizing ability was unsatisfactory because it only deodorized up to 100 ppm in 10 minutes against an initial concentration of 200 ppm.
[0076]
(Comparative Example 3)
Melt viscosity 3950 poise (262 ° C, 121.6 sec ^-1 ), N6 with a melting point of 220 ° C. and a melt viscosity of 560 poise (262 ° C., 121.6 sec) ^-1 ), And after PE blending with PE having a melting point of 105 ° C. so that the N6 blend ratio is 65% by weight, using the apparatus shown in FIG. 14, the temperature of the single-screw extrusion kneader 21 was melted at 260 ° C. Equation 12, discharge hole diameter 0.30 mm, discharge hole length. Melt spinning was carried out in the same manner as in Example 1 using a 50 mm barrel cap. However, the blend spots of N6 and PE were large, and not only a large ball was generated under the die, but also the threading property was poor, and the yarn could not be wound up stably. Thus, stretching and heat treatment were performed in the same manner as in Example 1 to obtain a stretched yarn of 82 dtex and 12 filaments. The draw ratio at this time was 2.0 times.
[0077]
Using this drawn yarn, a circular knitted fabric was formed in the same manner as in Example 1, and PE was eluted with toluene at 85 ° C. for 1 hour or more to remove 99% or more of PE. N6 single yarn was pulled out from the obtained circular knitted fabric, and the cross section of the fiber was observed by TEM. The single fiber diameter was 500 nm to 3 μm (single fiber fineness 2 × 10 ^-3 ~ 8x10 ^-2 dtex) was confirmed to be produced. The number average single fiber fineness is 9 × 10 ^-3 It was a large dtex (single yarn diameter 1.0 μm). Further, the single fiber fineness variation of the N6 ultrafine yarn was also large. The hygroscopicity of the circular knitted fabric using this super extra fine yarn was as low as 2%. Further, ammonia was deodorized as a test for removing harmful and offensive odorous substances. However, the deodorizing ability was unsatisfactory because it only deodorized up to 100 ppm in 10 minutes against an initial concentration of 200 ppm.
[0078]
(Comparative Example 4)
Melt viscosity 1500 poise (262 ° C, 121.6 sec ^-1 ), N6 with a melting point of 220 ° C. and a melt viscosity of 1450 poise (262 ° C., 121.6 sec) ^-1 16) A comparative example using the apparatus of FIG. 16 that leads PE to a biaxial extrusion kneader 23 while measuring each polymer using a chip metering device 24 so that the N6 blend ratio becomes 20% by weight with PE having a melting point of 105 ° C. In the same manner as in No. 3, melt spinning was performed. However, the blend spots of N6 and PE were large, and not only a large ball was generated under the die, but also the threading property was poor, and the yarn could not be wound up stably. Thus, stretching and heat treatment were performed in the same manner as in Example 1 to obtain a stretched yarn of 82 dtex and 12 filaments. The draw ratio at this time was 2.0 times.
[0079]
Using this drawn yarn, a circular knitted fabric was formed in the same manner as in Example 1, and PE was eluted with toluene at 85 ° C. for 1 hour or more to remove 99% or more of PE. N6 single yarn was pulled out from the obtained circular knitted fabric, and the cross section of the fiber was observed by TEM. The single fiber diameter was 100 nm to 1 μm (single fiber fineness 9 × 10 ^-Five ~ 9x10 ^-3 dtex) was confirmed to be produced. However, the single fiber fineness by the number average is 1 × 10. ^-3 It was as large as dtex (single fiber diameter 384 nm). Furthermore, this also showed a large variation in the single fiber fineness of the ultrafine yarn (see FIGS. 7 and 8). The hygroscopicity of the circular knitted fabric using this super extra fine yarn was as low as 2%. Further, ammonia was deodorized as a test for removing harmful and offensive odorous substances. However, the deodorizing ability was unsatisfactory because it only deodorized up to 105 ppm in 10 minutes against an initial concentration of 200 ppm.
[0080]
(Comparative Example 5)
A sea-island composite yarn was obtained in the same manner as in Comparative Example 1 using PS and PET described in Comparative Example 1, using the spinning pack and base shown in FIG. 11 of JP-B-60-28822. At this time, 2: 1 (weight ratio) blend polymer of PS and PET was used as the island component of the sea-island composite yarn, and PS was used as the sea component (the sea-island composite ratio was 1: 1 by weight). Specifically, in FIG. 11 of the publication, the A component is PET and the B and C components are PS. Then, this was treated with trichlorethylene in the same manner as in Comparative Example 1 to remove 99% or more of PS to obtain a super fine yarn. When the cross section of the fiber was observed, there was a very small amount of single fiber having a single fiber diameter of about 100 nm. However, since the dispersion of PET in PS was poor, the single fiber fineness based on the number average was 9 × 10. ^-Four The dtex (single fiber diameter: 326 nm) was large, and the single fiber fineness variation of the ultrafine yarn was also large (see FIGS. 9 and 10). The hygroscopic property of the circular knitted fabric using this super extra fine yarn was as low as 0.1%. In addition, an ammonia deodorization test was performed as a test for removing harmful and offensive odorous substances. However, the deodorization test was performed only up to 180 ppm in 10 minutes against the initial concentration of 200 ppm, and there was almost no deodorizing ability.
[0081]
(Comparative Example 6)
After making the knitting density sweet and making the polymer alloy fiber obtained in Example 1 into a circular knitted fabric, the basis weight is 15 g / m made of N6 nanofibers by alkali treatment as in Example 1. ² I got a circular knitted fabric. This was put in a washing net with a household washing machine and washed and dehydrated. However, it was noticeably deformed and inferior in dimensional stability.
[0082]
[Table 1]

[0083]
[Table 2]

[0084]
(Example 5)
The N6 and copolymerized PET used in Example 1 were separately melted at 270 ° C. using the apparatus of FIG. 15, and then the polymer melt was guided to the spin block 3 having a spinning temperature of 280 ° C. through the uniaxial kneader 21. . Then, using a static kneader 22 (trade name “High Mixer” manufactured by Toray Engineering Co., Ltd.) mounted in the spin pack 4, the two types of polymers were divided into 1.04 million and mixed well, and then melted in the same manner as in Example 1. Spinning was performed. The blend ratio of the polymer at this time was 20% by weight for N6 and 80% by weight for copolymerized PET. The undrawn yarn was drawn and heat treated in the same manner as in Example 1. The obtained polymer alloy fiber showed excellent properties of 120 dtex, 36 filaments, strength 3.9 cN / dtex, elongation 38%, U% = 1.7%. When the cross section of this polymer alloy fiber was observed by TEM, as in Example 1, copolymer PET was the sea and N6 was the island-island structure. The number average diameter of island N6 was 52 nm, and N6 was ultrafine. A dispersed polymer alloy fiber was obtained.
[0085]
Using the polymer alloy fiber obtained here, in the same manner as in Example 1, the basis weight of the nanofiber aggregate in the form of spun yarn by alkali treatment was 60 g / m. ² I got a circular knitted fabric. Furthermore, as a result of analyzing the single fiber fineness variation of these nanofibers in the same manner as in Example 1, the single fiber diameter by the number average of the nanofibers was 54 nm (3 × 10 ^-Five dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small (see Table 4).
[0086]
Further, the moisture absorption rate (ΔMR) of the circular knitted fabric made of the nanofiber aggregate was 6%. Further, the yarn composed of this N6 nanofiber aggregate had a strength of 2.0 cN / dtex and an elongation of 50%. Furthermore, the shrinkage percentage at 140 ° C. dry heat was 3%. Furthermore, when buffing was performed on this circular knitted fabric, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin. Further, the circular knitted fabric without buffing is immersed in a 10 wt% aqueous solution of Silcote PP (specially modified silicone / trade name, manufactured by Matsumoto Yushi Co., Ltd.), and the processing liquid is circular knitted so that the pickup rate of the aqueous solution is 150%. Granted to the ground. After applying the treatment liquid, it was dried in an oven at 110 ° C. for 3 minutes in a relaxed state. After drying, the cloth was treated and showed a delicate touch different from buffing and a moist and fresh texture like human skin. Further, there was a feeling of cool contact. Moreover, these circular knitted fabrics were put into a washing net by a household washing machine and washed and dehydrated, but they did not lose shape and showed good dimensional stability.
[0087]
(Example 6)
N6 and copolymerized PET used in Example 1 were melt-kneaded with a 270 ° C. biaxial extrusion kneader 23 using the apparatus shown in FIG. 16, and then the polymer melt was guided to the spin block 3 with a spinning temperature of 280 ° C. . Then, melt spinning was performed in the same manner as in Example 1. The blend ratio of the polymer at this time was 20% by weight for N6 and 80% by weight for copolymerized PET. The undrawn yarn was drawn and heat treated in the same manner as in Example 1. The obtained polymer alloy fiber showed excellent properties of 120 dtex, 36 filaments, strength 3.9 cN / dtex, elongation 38%, U% = 1.7%. When the cross section of this polymer alloy fiber was observed by TEM, as in Example 1, copolymer PET was the sea, N6 was the island-island structure, and the number average diameter of the island N6 was 54 nm, and N6 exceeded A finely dispersed polymer alloy fiber was obtained.
[0088]
Using the polymer alloy fiber obtained here, in the same manner as in Example 1, the basis weight of the nanofiber aggregate in the form of spun yarn by alkali treatment was 60 g / m. ² Got a circular knitting. Furthermore, as a result of analyzing the single fiber fineness variation of these nanofibers in the same manner as in Example 1, the single fiber diameter based on the number average of the nanofibers was 56 nm (3 × 10 ^-Five dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small (see Table 4).
[0089]
Further, the moisture absorption rate (ΔMR) of the circular knitted fabric made of the nanofiber aggregate was 6%. Further, the yarn composed of this N6 nanofiber aggregate had a strength of 2.0 cN / dtex and an elongation of 50%. Furthermore, the shrinkage percentage at 140 ° C. dry heat was 3%. Furthermore, when buffing was performed on this circular knitted fabric, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin. Further, the circular knitted fabric without buffing is immersed in a 10 wt% aqueous solution of Silcote PP (specially modified silicone / trade name, manufactured by Matsumoto Yushi Co., Ltd.), and the treatment liquid is circular knitted so that the pickup rate of the aqueous solution is 150%. Was granted. After applying the treatment liquid, it was dried in an oven at 110 ° C. for 3 minutes in a relaxed state. After drying, the cloth was treated and showed a delicate touch different from buffing and a moist and fresh texture like human skin. Further, there was a feeling of cool contact.
[0090]
Moreover, these circular knittings were put into a washing net by a household washing machine and washed and dehydrated. However, they did not deform and showed good dimensional stability.
[0091]
[Table 3]

[0092]
[Table 4]

[0093]
(Example 7)
Copolymerized PET is a hot water-soluble polymer of a polyalkylene glycol derivative, registered trademark “Paogen PP-15” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (melt viscosity 3500 poise, 262 ° C., 121.6 sec. ^-1 The melting point was changed to 55 ° C., the shear stress between the base wall and the polymer was 0.075 MPa, the spinning speed was 5000 m / min, and the mixture was kneaded and melt-spun in the same manner as in Example 1. The obtained polymer alloy fiber showed excellent properties of 70 dtex, 36 filaments, strength 3.8 cN / dtex, elongation 50%, U% = 1.7%. When the cross section of this polymer alloy fiber was observed with a TEM, it was found that the hot water soluble polymer was the sea, N6 was the island-island structure, the number average diameter of the island N6 was 53 nm, and the polymer with N6 ultra-dispersed. Alloy fibers were obtained.
[0094]
Using the polymer alloy fiber obtained here, the basis weight was 60 g / m by alkali treatment in the same manner as in Example 1. ² A circular knitted fabric composed of N6 nanofiber aggregates was obtained. Furthermore, as a result of analyzing the single fiber fineness variation of these nanofibers in the same manner as in Example 1, the single fiber diameter based on the number average of the nanofibers was 56 nm (3 × 10 ^-Five dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small (see Table 6). Further, the moisture absorption rate (ΔMR) of the circular knitted fabric made of the nanofiber aggregate was 6%. Further, the yarn composed of this N6 nanofiber aggregate had a strength of 2.0 cN / dtex and an elongation of 60%.
[0095]
Furthermore, when buffing was performed on this circular knitted fabric, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin. Further, the circular knitted fabric without buffing is immersed in a 10 wt% aqueous solution of Silcote PP (specially modified silicone / trade name, manufactured by Matsumoto Yushi Co., Ltd.), and the processing liquid is circular knitted so that the pickup rate of the aqueous solution is 150%. Granted to the ground. After applying the treatment liquid, it was dried in an oven at 110 ° C. for 3 minutes in a relaxed state. After drying, the cloth was treated and showed a delicate touch different from buffing and a moist and fresh texture like human skin. Further, there was a feeling of cool contact. In addition, these circular knitted fabrics were put into a washing net by a household washing machine and washed and dehydrated. However, they did not lose shape and showed good dimensional stability.
[0096]
(Example 8)
Instead of N6, melt viscosity 1000 poise (280 ° C., 121.6 sec. ^-1 15) Using N66 having a melting point of 250 ° C., using the apparatus of FIG. 15, N66 was melted at 270 ° C., and the hot water-soluble polymer used in Example 7 was melted at 80 ° C., and then the polymer melt was spun at 280 ° C. It led to the spin block 3. Then, melt spinning was performed in the same manner as in Example 5. The polymer blend ratio at this time was 20% by weight for N66, 80% by weight for the hot water-soluble polymer, and the discharge rate per single hole was 1.0 g / min. The spinning speed at this time was 5000 m / min, and the shear stress between the die hole wall and the polymer was 0.062 MPa, which was sufficiently low. Then, a polymer alloy fiber having 70 dtex, 36 filaments, strength 4.5 cN / dtex, and elongation 45% was obtained. When the cross section of the obtained polymer alloy fiber was observed with a TEM, the hydrothermally soluble polymer was the sea, N66 was the island-island structure, the number average diameter of the island N66 was 58 nm, and N66 was very finely dispersed. A polymer alloy fiber was obtained.
[0097]
Using the polymer alloy fiber obtained here, the basis weight was 60 g / m by alkali treatment in the same manner as in Example 1. ² A circular knitted fabric composed of N6 nanofiber aggregates was obtained. Furthermore, as a result of analyzing the single fiber fineness variation of these nanofibers in the same manner as in Example 1, the single fiber diameter by the number average of the nanofibers was 62 nm (3 × 10 ^-Five dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small (see Table 6).
[0098]
Further, the moisture absorption rate (ΔMR) of the circular knitted fabric made of the nanofiber aggregate was 6%. Further, the yarn composed of this N6 nanofiber aggregate had a strength of 2.5 cN / dtex and an elongation of 60%. Furthermore, when buffing was performed on this circular knitted fabric, it showed a super peach feeling that was not possible with conventional ultra-fine fibers and a moist and fresh texture like human skin. Further, the circular knitted fabric without buffing is immersed in a 10 wt% aqueous solution of Silcote PP (specially modified silicone / trade name, manufactured by Matsumoto Yushi Co., Ltd.), and the processing liquid is circular knitted so that the pickup rate of the aqueous solution is 150%. Granted to the ground. After applying the treatment liquid, it was dried in an oven at 110 ° C. for 3 minutes in a relaxed state. After drying, the cloth was treated and showed a delicate touch different from buffing and a moist and fresh texture like human skin. Further, there was a feeling of cool contact. In addition, these circular knitted fabrics were put into a washing net by a household washing machine and washed and dehydrated. However, they did not lose shape and showed good dimensional stability.
[0099]
Example 9
Melt viscosity 3000 poise (262 ° C, 121.6 sec ^-1 ), A copolymerized PET having a melting point of 225 ° C. (8% by weight of PEG 1000 and 7 mol% of isophthalic acid) and the hot water-soluble polymer used in Example 8 were kneaded and melt-spun in the same manner as in Example 6. At this time, the polymer blend ratio was 20% by weight for copolymerized PET, 80% by weight for hot water-soluble polymer, the discharge rate per single hole was 1.0 g / min, and the spinning speed was 6000 m / min. At this time, the shear stress between the die hole wall and the polymer was 0.078 MPa, which was sufficiently low. A polymer alloy fiber having 60 dtex, 36 filaments, a strength of 3.0 cN / dtex, and an elongation of 55% was obtained. When the cross section of the obtained polymer alloy fiber was observed with a TEM, the water-soluble polymer showed the sea and the copolymerized PET showed the island-island structure, and the number average diameter of the island-copolymerized PET was 52 nm. A polymer alloy fiber in which PET was ultrafinely dispersed was obtained.
[0100]
After the circular knitted fabric was prepared in the same manner as in Example 1 using the polymer alloy fibers obtained here, the hot water soluble polymer was eluted with hot water at 100 ° C. 60g / m with a nanofiber aggregate having a dry feeling ² I got a circular knitted fabric. As a result of analyzing the single fiber fineness variation of the nanofiber in the same manner as in Example 1, the single fiber diameter by the number average of the nanofiber is 54 nm (3 × 10 ^-Five dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small (see Table 6). The circular knitted fabric composed of this copolymerized PET nanofiber assembly was immersed in a 3% aqueous solution of diethylenetriamine at 50 ° C. for 1 minute to support the diethylenetriamine on the nanofiber. When this hydrogen sulfide removal was evaluated, the concentration decreased from 30 ppm to 1 ppm in 10 minutes, and an excellent removal capability was exhibited. Moreover, an A4-sized deodorizing sheet was produced using this circular knitted fabric, and was washed and dehydrated by putting it in a washing net with a household washing machine. However, it did not deform and showed good dimensional stability.
[0101]
(Example 10)
Melt viscosity 1900 poise (280 ° C., 121.6 sec ^-1 ), PET having a melting point of 255 ° C. and the hot water-soluble polymer used in Example 7 were kneaded and melt-spun in the same manner as in Example 9. At this time, the polymer blend ratio was 20% by weight for PET, 80% by weight for hot water-soluble polymer, the melting temperature for PET was 285 ° C, the melting temperature for hot water-soluble polymer was 80 ° C, and the discharge amount per single hole was 1%. 0.0 g / min. At this time, the shear stress between the die hole wall and the polymer was 0.080 MPa and sufficiently low. A polymer alloy fiber having 60 dtex, 36 filaments, a strength of 3.0 cN / dtex, and an elongation of 45% was obtained. When the cross section of the obtained polymer alloy fiber was observed with a TEM, the water-soluble polymer was the sea, and PET was the island-island structure. The number average diameter of the island PET was 62 nm, and the PET was finely dispersed. A polymer alloy fiber was obtained.
[0102]
Using the polymer alloy fiber obtained here, the basis weight of 60 g / m consisting of a nanofiber aggregate was obtained in the same manner as in Example 9. ² I got a circular knitted fabric. The number average single fiber diameter of the nanofiber is 65 nm (3 × 10 ^-Five dtex), which is an unprecedented fineness, and the single yarn fineness variation was very small (see Table 6). The circular knitted fabric made of this PET nanofiber assembly was immersed in a 3% aqueous solution of diethylenetriamine at 50 ° C. for 1 minute, thereby supporting the diethylenetriamine on the nanofiber. When this hydrogen sulfide removal was evaluated, the concentration decreased from 30 ppm to 1 ppm in 10 minutes, and an excellent removal capability was exhibited. Moreover, an A4-sized deodorizing sheet was produced using this circular knitted fabric, and was washed and dehydrated by putting it in a washing net with a household washing machine. However, it did not deform and showed good dimensional stability.
[0103]
(Example 11)
Melt viscosity 1200 poise (262 ° C, 121.6 sec ^-1 ), PBT having a melting point of 225 ° C. and the hot water-soluble polymer used in Example 7 were kneaded and melt-spun in the same manner as in Example 9. At this time, the polymer blend ratio was 20% by weight of PET, 80% by weight of hot water soluble polymer, the melting temperature of PBT was 255 ° C, the melting temperature of hot water soluble polymer was 80 ° C, the spinning temperature was 265 ° C, and the single pore The per unit discharge amount was 1.0 g / min. At this time, the shear stress between the base hole wall and the polymer was sufficiently low at 0.075 MPa. A polymer alloy fiber having 60 dtex, 36 filaments, a strength of 3.0 cN / dtex, and an elongation of 45% was obtained. When the cross section of the obtained polymer alloy fiber was observed by TEM, the hydrothermally soluble polymer was the sea, the PBT was the island-island structure, the number average diameter of the island PBT was 62 nm, and the PBT was finely dispersed. A polymer alloy fiber was obtained.
[0104]
Using the polymer alloy fiber obtained here, the basis weight of 60 g / m consisting of a nanofiber aggregate was obtained in the same manner as in Example 9. ² I got a circular knitted fabric. The number average single fiber diameter of this nanofiber is 65 nm (4 × 10 4 ^-Five dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small (see Table 6). The circular knitted fabric composed of the PBT nanofiber aggregate was immersed in a 3% aqueous solution of diethylenetriamine at 50 ° C. for 1 minute to support the diethylenetriamine on the nanofiber. When this hydrogen sulfide removal was evaluated, the concentration decreased from 30 ppm to 1 ppm in 10 minutes, and an excellent removal capability was exhibited. Moreover, an A4-sized deodorizing sheet was produced using this circular knitted fabric, and was washed and dehydrated by putting it in a washing net with a household washing machine. However, it did not deform and showed good dimensional stability.
[0105]
(Example 12)
Melt viscosity 2200 poise (262 ° C., 121.6 sec ^-1 ), PTT having a melting point of 225 ° C. and the hot water-soluble polymer used in Example 7 were kneaded and melt-spun in the same manner as in Example 9. At this time, the shear stress between the die hole wall and the polymer was 0.073 MPa, which was sufficiently low. A polymer alloy fiber having 60 dtex, 36 filaments, a strength of 3.0 cN / dtex, and an elongation of 45% was obtained. When the cross section of the obtained polymer alloy fiber was observed with TEM, the water-soluble polymer showed the sea-island structure, the PTT was the island-island structure, the diameter of the island PTT was 62 nm, and the PTT was very finely dispersed. A polymer alloy fiber was obtained.
[0106]
Using the polymer alloy fiber obtained here, the basis weight of 60 g / m consisting of a nanofiber aggregate was obtained in the same manner as in Example 9. ² I got a circular knitted fabric. The number average single fiber diameter of this nanofiber is 65 nm (4 × 10 4 ^-Five dtex), which is an unprecedented fineness, and the single fiber fineness variation was very small (see Table 6). The circular knitted fabric made of the PTT nanofiber aggregate was immersed in a 3% aqueous solution of diethylenetriamine at 50 ° C. for 1 minute to support the diethylenetriamine on the nanofiber. When this hydrogen sulfide removal was evaluated, the concentration decreased from 30 ppm to 1 ppm in 10 minutes, and an excellent removal capability was exhibited. Moreover, an A4-sized deodorizing sheet was produced using this circular knitted fabric, and was washed and dehydrated by putting it in a washing net with a household washing machine. However, it did not deform and showed good dimensional stability.
[0107]
(Example 13)
Melt viscosity 3500 poise (220 ° C, 121.6 sec ^-1 ) PLA having a melting point of 170 ° C. and the hot water-soluble polymer used in Example 7 were kneaded and melt-spun in the same manner as in Example 9. The polymer blend ratio was 20 wt% PLA, 80 wt% hot water soluble polymer, spinning temperature 235 ° C., die surface temperature 220 ° C., and the discharge rate per single hole was 1.0 g / min. At this time, the shear stress between the die hole wall and the polymer was 0.080 MPa and sufficiently low. A polymer alloy fiber having 60 dtex, 36 filaments, a strength of 2.5 cN / dtex, and an elongation of 35% was obtained. When the cross section of the obtained polymer alloy fiber was observed with TEM, the hydrothermally soluble polymer was the sea, PLA was the island-island structure, the number average diameter of the island PLA was 48 nm, and the PLA was finely dispersed. A polymer alloy fiber was obtained.
[0108]
Using the polymer alloy fiber obtained here, the basis weight of 60 g / m consisting of a nanofiber aggregate was obtained in the same manner as in Example 9. ² I got a circular knitted fabric. The number average single fiber diameter of the nanofiber is 50 nm (2 × 10 ^-Five dtex), which is an unprecedented fineness, and the single yarn fineness variation was very small (see Table 6). The circular knitted fabric composed of this PLA nanofiber aggregate was immersed in a 3% aqueous solution of diethylenetriamine at 50 ° C. for 1 minute to support the diethylenetriamine on the nanofiber. When this hydrogen sulfide removal was evaluated, the concentration decreased from 30 ppm to 1 ppm in 10 minutes, and an excellent removal capability was exhibited. Moreover, an A4 size deodorant sheet was produced using this circular knitted fabric, and it was put into a washing net and washed and dehydrated by a household washing machine. However, it did not deform and showed good dimensional stability.
[0109]
[Table 5]

[0110]
[Table 6]

[0111]
(Comparative Example 7)
A circular knitted fabric is produced using the PS / PET sea-island composite yarn produced in Comparative Example 1, and PS is removed in the same manner as in Comparative Example 1, and a circular knitted fabric made of PET ultrafine yarn having a single fiber fineness of 0.04 dtex ( 150 g / m ² ) This circular knitted fabric made of PET ultrafine yarn was immersed in a 3% aqueous solution of diethylenetriamine at 50 ° C. for 1 minute to carry diethylenetriamine on the PET ultrafine yarn, but it could hardly be carried. When this hydrogen sulfide removal was evaluated, the concentration decreased only from 30 ppm to 15 ppm in 10 minutes, and the hydrogen sulfide removal ability was insufficient.
[0112]
(Example 14)
Silicone-treated basis weight 150 g / m prepared in Example 2 ² T-shirts were produced using circular knitted fabric made of N6 nanofibers, but they were very comfortable due to the touch like human skin and had a healing effect. Moreover, this was put into a washing net with a household washing machine and washed and dehydrated, but it did not lose its shape and showed good dimensional stability.
[0113]
(Example 15)
Silicone-treated basis weight 100 g / m prepared in Example 3 ² Women's shorts were made using circular knitted fabric made of N6 nanofiber, but it was very comfortable due to the touch like human skin and had a healing effect. Moreover, this was put into a washing net with a household washing machine and washed and dehydrated, but it did not lose its shape and showed good dimensional stability.
[0114]
(Example 16)
Silicone-treated basis weight 150 g / m prepared in Example 4 ² A shirt for women was produced using a fabric made of N6 nanofiber, but it was very comfortable due to the touch like a human skin, and also had a healing effect. Moreover, this was put into a washing net with a household washing machine and washed and dehydrated, but it did not lose its shape and showed good dimensional stability.
did.
[0115]
(Example 17)
Using a circular knitted fabric made of N6 nanofibers produced in Example 1 and Example 2 and the fabric produced in Example 4, an A4-sized deodorant sheet was produced, and ammonia and a test for removing harmful and offensive odorous substance gases were made. When the deodorization test of acetic acid and hydrogen sulfide was conducted, it showed an excellent deodorization ability (toxic substance adsorption ability) as compared with a normal fineness nylon thread (44 dtex, 12 filaments) (see Tables 7 to 9). ).
[0116]
[Table 7]

[0117]
[Table 8]

[0118]
[Table 9]

[0119]
(Example 18)
Using the N6 / copolymerized PET alloy false twisted yarn produced in Example 3 as a sheath yarn, “Lycra” (registered trademark), which is a polyurethane fiber yarn manufactured by Toray Industries, Inc., was covered. And after producing the knitted fabric for tights using this covering yarn, the alkali treatment was performed like Example 3 and the knitted fabric for tights which consists of nanofibers was produced. The fabric weight of this tights knitted fabric is 100g / m ² The weight ratios of N6 nanofibers and polyurethane fiber yarns were 90% and 10%, respectively. This was immersed in a 10 wt% aqueous solution of Silcote PP (specially modified silicone / trade name, manufactured by Matsumoto Yushi Co., Ltd.), and the treatment solution was applied to the knitted fabric so that the pickup rate of the aqueous solution was 150%. After applying the treatment liquid, it was dried in an oven at 110 ° C. for 3 minutes in a relaxed state. After drying, a spreading treatment was performed. And this knitted fabric for tights was sewn, and tights were produced. The tights had a delicate touch and a moist and fresh texture like human skin, and were extremely comfortable to wear.
[0120]
(Example 19)
Melt spinning was carried out in the same manner as in Example 2 at a speed (spinning speed) of the first take-up roller 9 of 3500 m / min to obtain 400 dtex, 96 filament N6 / copolymerized PET polymer alloy fibers. The strength of this polymer alloy fiber was 2.5 cN / dtex, the elongation was 100%, and U% was 1.9%. And the drawing false twist was given to this using the apparatus of FIG. 18, and the false twisted yarn of 333 dtex and 96 filaments was obtained. At this time, a urethane disk was used as the rotor 33, the temperature of the heater 31 was 180 ° C., and the draw ratio was 1.2 times. The obtained false twisted yarn had a strength of 3.0 cN / dtex and an elongation of 32%.
[0121]
The false twisted yarn was subjected to a sweet twist of 300 turns / m, and a 2/2 twill woven fabric was produced by using an S twist / Z twist double yarn for warp and weft. Then, the twill fabric obtained was subjected to alkali treatment in the same manner as in Example 1, and the basis weight was 150 g / m made of N6 nanofibers. ² The curtain fabric was obtained. Furthermore, as a result of analyzing the single fiber fineness variation of these nanofibers in the same manner as in Example 1, the single fiber diameter based on the number average of nanofibers was 86 nm (6 × 10 6 ^-Five dtex) and unprecedented fineness, and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. The N6 nanofiber false twisted yarn had a strength of 2.0 cN / dtex and an elongation of 40%.
[0122]
Further, when this curtain fabric was subjected to silicone treatment in the same manner as in Example 2, it showed a delicate touch and a moist and fresh texture like human skin. Further, there was a feeling of cool contact. Further, the moisture absorption rate (ΔMR) thereof was 6%, indicating sufficient moisture absorption. When the deodorization test for acetic acid was performed, the concentration decreased from 100 ppm to 1 ppm in 10 minutes, and excellent deodorization property was exhibited. And when this fabric was used to produce a curtain and suspended between 6 tatami mats, it was possible to create a refreshing indoor environment and to suppress condensation. The curtain was put into a washing net with a household washing machine and washed and dehydrated, but it did not deform and showed good dimensional stability.
[0123]
(Example 20)
Similar to the N6 / copolymerized PET alloy polymer used in Example 2, the melt viscosity of 5000 poise (262 ° C., shear rate of 121.6 sec) used in Example 2 was used. ^-1 ), N6 having a melting point of 220 ° C. was melted separately, and core-sheath composite spinning was carried out in the same manner as in Example 2 using a die having a discharge hole of Y type. At this time, the core component was alloy polymer, the sheath component was N6, and the core component composite ratio was 50% by weight. The spun yarn is taken up at 800 m / min, then stretched in two stages under the condition that the first stage draw ratio is 1.3 times and the total ratio is 3.5 times, and further crimped using a jet nozzle. Thereafter, a bulky processed yarn of 500 dtex and 90 filaments was wound up. The bulky processed yarn had a strength of 5.2 cN / dtex and an elongation of 25%.
[0124]
Two of the resulting bulky processed yarns are drawn together and twisted, then twisted at the bottom (200 T / m), twisted together with the two at the top twist (200 T / m), and twisted at a dry heat of 170 ° C. Then, it was tufted by a known method as a cut pile carpet. At this time, with a normal level cut, 1/10 gauge, basis weight 1500 g / m ² The stitch was adjusted so that Thereafter, backing was performed. At the time of tufting, a woven base fabric using a blended yarn of acrylic fiber and polyester fiber was used as the base fabric. Furthermore, only the cut pile portion was treated with alkali to develop a structure in which the cut pile portion was wrapped with N6 nanofibers. In addition, the number average single fiber diameter of the obtained N6 nanofibers was 86 nm (6 × 10 6 ^-Four dtex), and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. As a result, the basis weight of the cut pile portion is 1200 g / m. ² Thus, the weight fraction of N6 nanofibers was 33% by weight for the cut pile portion and 15% by weight for the entire carpet. This carpet had no problem in hair fall because the cut pile portion held the N6 nanofibers by the sheath component N6. In addition, since N6 nanofibers contained 15% by weight with respect to the entire carpet, sufficient humidity control and deodorization were exhibited, a refreshing indoor environment could be achieved, and condensation could also be suppressed. .
[0125]
(Example 21)
After four N6 / copolymerized PET alloy false twisted yarns obtained in Example 19 were combined, they were used as warps and wefts to weave a 2/2 twill fabric, and then as in Example 21 200g / m per unit area of N6 nanofiber false twisted yarn by alkali treatment ² A seat skin for interior was prepared. Furthermore, as a result of analyzing the single fiber fineness variation of the NN6 nanofiber in the same manner as in Example 1, the single fiber diameter by the average number of nanofibers was 86 nm (6 × 10 ^-Five dtex) and unprecedented fineness, and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. When this was used for the skin of a chair, it was not only soft and comfortable, but also showed sufficient humidity control and deodorization, and a refreshing indoor environment could be achieved.
[0126]
(Example 22)
As with the N6 / copolymerized PET alloy polymer used in Example 2, the melt viscosity of 5000 poise (262 ° C., shear rate of 121.6 sec) used in Example 2 was used. ^-1 ), N6 having a melting point of 220 ° C. was melted separately, and core-sheath composite spinning was carried out in the same manner as in Example 2 using a round hole cap. At this time, the core component was alloy polymer, the sheath component was N6, and the core component composite ratio was 30% by weight. This was taken up at 1600 m / min and wound up once, and then stretched at a temperature of the first hot roller 17 of 90 ° C., a temperature of the second hot roller 18 of 130 ° C., and a stretching ratio of 2.7 times. The obtained polymer alloy fiber was 220 dtex, 144 filaments, strength = 4.8 cN / dtex, elongation = 35%, U% = 1.9%. And this was subjected to a sweet twist of 300 turns / m, and a plain woven fabric was produced using the background. Then, an alkali treatment was applied in the same manner as in Example 2, and the basis weight was 220 g / m consisting of a fiber in which N6 nanofibers were covered with sheath component N6 ² Fabric was obtained. In addition, the number average single fiber diameter of the obtained N6 nanofibers was 86 nm (6 × 10 6 ^-Four dtex), and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. Further, when the silicone treatment was applied to this as in Example 2, it showed a delicate touch and a moist and fresh texture like human skin. And, a futon cover and a sheet were produced using this, but it was very comfortable because of its excellent texture and hygroscopicity. Furthermore, the odor could be suppressed even if there was incontinence due to its excellent deodorant properties. Moreover, these beddings were put into a washing net by a household washing machine and washed and dehydrated. However, they were not deformed and showed good dimensional stability.
[0127]
(Example 23)
Core-sheath composite spinning was carried out in the same manner as in Example 22 at a speed of the first take-up roller 9 of 3500 m / min to obtain 264 dtex, 144 filament N6 / copolymerized PET polymer alloy fiber. The strength of this polymer alloy fiber was 3.5 cN / dtex, the elongation was 110%, and U% was 1.9%. 18 was stretched false twisted using the apparatus shown in FIG. 18 to obtain a false twisted yarn of 220 dtex and 144 filaments. At this time, a urethane disk was used as the rotor 33, the temperature of the heater 31 was 180 ° C., and the draw ratio was 1.2 times. The obtained false twisted yarn had a strength of 4.1 cN / dtex and an elongation of 32%.
[0128]
The false twisted yarn was subjected to a sweet turn of 300 turns / m, and a plain fabric was produced using the warp and the weft. Then, this was subjected to alkali treatment in the same manner as in Example 1, and a basis weight of 100 g / m made of N6 nanofibers. ² A woven fabric composed of fibers in which N6 nanofibers were covered with a sheath component N6 was obtained. Furthermore, as a result of analyzing the single fiber fineness variation of these nanofibers in the same manner as in Example 1, the single fiber diameter based on the number average of nanofibers was 86 nm (6 × 10 6 ^-Five dtex) and unprecedented fineness, and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. This woven fabric had a structure in which N6 nanofibers were encapsulated in N6 hollow fibers, and exhibited a soft and elastic excellent texture like marshmallow. Further, the false twisted yarn containing this N6 nanofiber had a strength of 2.9 cN / dtex and an elongation of 41%.
[0129]
When this fabric was treated with silicone in the same manner as in Example 2, it showed a delicate touch and a moist and fresh texture like human skin. Further, there was a feeling of cool contact. Further, the moisture absorption rate (ΔMR) of this was 6%, indicating a sufficient moisture absorption. A shirt for women was produced using this fabric, which was very comfortable and had a healing effect. This shirt was washed and dewatered without putting it in a washing net with a household washing machine. However, it did not lose its shape, and N6 nanofibers were encapsulated with N6 hollow fibers, which showed even better dimensional stability.
[0130]
(Example 24)
A plain woven fabric was produced using the polymer alloy fibers produced in Example 2 as warp and weft. Then, the alkali treatment is performed in the same manner as in Example 2, and the basis weight of the nanofiber aggregate is 250 g / m. ² A plain woven fabric was obtained. Furthermore, as a result of analyzing the single fiber fineness variation of these nanofibers in the same manner as in Example 1, the single fiber diameter by the average number of nanofibers was 86 nm (6 × 10 6 ^-Five dtex) and unprecedented fineness, and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. This fabric exhibited unique tackiness when immersed in water. And this was buffed. This has better wiping performance than the conventional wiping cloth using ultrafine yarn, and is suitable as a wiping cloth. In addition, this was put into a washing net with a household washing machine and washed and dehydrated, but it did not deform and showed good dimensional stability.
[0131]
(Example 25)
The polymer alloy fiber produced in Example 2 was subjected to mechanical crimping, then cut to a fiber length of 51 mm, defibrated with a card, and then made into a web with a cross wrap weber. Next, using a needle punch, the basis weight is 750 g / m. ² The fiber entangled nonwoven fabric. Further, a fiber entangled nonwoven fabric is impregnated with a liquid comprising 13% by weight of a polyurethane composition (PU) mainly composed of polyether polyurethane (PU) and 87% by weight of N, N′-dimethylformamide (DMF), The PU was coagulated in a 40% by weight aqueous solution of DMF and then washed with water. Further, this non-woven fabric was subjected to an alkali treatment with a 3% aqueous sodium hydroxide solution (60 ° C., bath ratio 1: 100) for 2 hours to remove 99% or more of the copolymerized PET, and N6 having a PU content of 40% by weight. A polishing substrate comprising a nanofiber structure composed of a nanofiber assembly and PU was obtained. Furthermore, as a result of analyzing the single fiber fineness variation of these nanofibers in the same manner as in Example 1, the single fiber diameter by the average number of nanofibers was 86 nm (6 × 10 6 ^-Five dtex) and unprecedented fineness, and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. The content of N6 nanofibers in the polishing substrate is 70% by weight, and the basis weight of the N6 nanofiber nonwoven fabric is 325 g / m. ² Met. After cutting this into two parts, the surface was buffed with JIS # 240, # 350, # 500 sandpaper. Further, this was nipped by two upper and lower heated rollers with a surface temperature of 150 ° C. with a gap of 1.0 mm, and 0.7 kg / cm ² Was pressed with a cooling roller having a surface temperature of 15 ° C. to obtain a polishing cloth having a smooth surface. The results of evaluation of this polishing cloth by the following method are shown in Table 10. The polishing cloth has a higher smoothness of the object to be polished and has fewer scratches, which is a defect, as compared with the conventional method using super extra fine yarn. The characteristics are shown. Furthermore, since the basis weight was sufficiently large, the polishing cloth was not torn during polishing and the workability was good.
[0132]
<Polishing Evaluation: Hard Disk Texturing>
Object to be polished: Substrate obtained by polishing a commercially available aluminum plate after Ni-P plating
(Average surface roughness = 0.28 nm)
Polishing conditions: The substrate was attached to a texture device and polished under the following conditions. Abrasive grain: Free abrasive slurry of diamond with an average particle diameter of 0.1 μm
Drip rate: 4.5 ml / min
Rotation speed: 1000rpm
Tape speed: 6 cm / min
Polishing conditions: Amplitude 1 mm-lateral vibration 300 times / minute
Number of evaluation sheets: 30 substrates / level
<Average surface roughness Ra of the object to be polished>
Using a Veeco original yarn force microscope (AFM) with a soundproofing device installed in a clean room with a temperature of 20 ° C and a relative humidity of 50%, the surface roughness of 30 substrates / level was measured and the average surface was measured. The roughness Ra is obtained. The measurement range is based on the center of the disk of each substrate, two central points of the radius are selected symmetrically, and the measurement is performed at an area of 5 μm × 5 μm.
[0133]
<Number of scratches>
The surface is observed with an interference microscope manufactured by ZYGO, and the number of surface scratches (X) of each sample is measured. Scratches with a size of 0.1 μm × 100 μm or more are counted. This is measured for 30 substrates / level, and the number of scratches β is defined from the score y based on the number of scratches.
When X ≦ 4 y = X
When X ≧ 5, y = 5
β = Σy _i (I = 1-30)
Where Σy _i Is the total number of scratches for 30 samples.
[0134]
(Comparative Example 8)
N6 nanofiber weight per unit area of 15g / m ² (The basis weight of the fiber-entangled nonwoven fabric is 30 g / m ² As in Example 25, a polishing cloth was prepared and a polishing test was performed. However, since the basis weight was too small, there was a problem that tearing occurred during polishing.
[0135]
(Comparative Example 9)
The N6 / PE blend fiber produced in Comparative Example 3 was subjected to mechanical crimping, then cut to a fiber length of 51 mm, opened with a card, and then made into a web with a cross wrap weber. Next, using a needle punch, the basis weight is 500 g / m. ² The fiber entangled nonwoven fabric. Furthermore, 13% by weight polyurethane composition mainly composed of polyether polyurethane (PU) and 87% by weight N, N'-dimethylformamide (DMF) are impregnated to solidify PU in 40% by weight DMF aqueous solution. After washing with water. Further, this nonwoven fabric was subjected to Parkren treatment to obtain an abrasive base material composed of a nanofiber structure composed of N6 ultrafine yarn and PU. Using this, a polishing cloth was obtained in the same manner as in Example 25. And when this abrasive cloth was evaluated, Ra = 1.6 nm, β = 32 and the smoothness of the object to be polished was lower than that using the nanofiber assembly, and the number of scratches, which is a defect, increased. Inferior polishing characteristics. The results are shown in Table 10.
[0136]
[Table 10]

[0137]
(Example 26)
The polymer alloy fibers produced in Example 1 and Examples 2, 5, and 6 were subjected to mechanical crimping, then cut to a fiber length of 51 mm, defibrated with a card, and then made into a web with a cross-wrap weber. Next, using a needle punch, the basis weight is 750 g / m. ² The fiber entangled nonwoven fabric. Further, a 13% by weight polyurethane composition mainly composed of polyether polyurethane (PU) and 87% by weight N, N′-dimethylformamide (DMF) were impregnated, and PU was added in a 40% by weight DMF aqueous solution. After coagulation, it was washed with water. Furthermore, this nonwoven fabric was subjected to an alkali treatment with a 3% aqueous sodium hydroxide solution (60 ° C., bath ratio 1: 100) for 2 hours to remove 99% or more of the copolymerized PET, and consisted of an N6 nanofiber aggregate and PU. A nanofiber structure having a thickness of about 1 mm was obtained. The number average diameters of N6 nanofibers were 60, 86, 61 and 61 nm, respectively. The N6 nanofiber content in this structure is 50, 70, 50 and 50% by weight, respectively, and the basis weight of the N6 nanofiber nonwoven fabric is 150, 325, 150 and 150 g / m, respectively. ² Met. After buffing one side of this nonwoven fabric with sandpaper to a thickness of 0.8 mm, the other side is treated with an emery buffing machine to form nanofiber aggregate raised surfaces, and further dyeing and finishing. Suede-like artificial leather was obtained. The obtained product had a very good appearance, no staining spots, and no problem in mechanical properties. In addition, the touch was softer and finer than the conventional artificial leather using ultra-fine yarn. Moreover, since it is also excellent in hygroscopicity, it has an excellent texture that also has a freshness like human skin that cannot be possessed by conventional artificial leather.
[0138]
(Comparative Example 10)
The N6 / PE blend fiber produced in Comparative Example 3 was subjected to mechanical crimping, then cut to a fiber length of 51 mm, defibrated with a card, and then made into a web with a cross wrap weber. Next, using a needle punch, the basis weight is 500 g / m. ² The fiber entangled nonwoven fabric. Further, a 13% by weight polyurethane composition mainly composed of polyether polyurethane (PU) and 87% by weight N, N′-dimethylformamide (DMF) were impregnated, and PU was added in a 40% by weight DMF aqueous solution. After coagulation, it was washed with water. Further, the nonwoven fabric was subjected to a parkren treatment to obtain a nanofiber structure having a thickness of about 1 mm made of N6 superfine yarn and PU. After buffing one side of this nanofiber structure with sandpaper to a thickness of 0.8 mm, the other side is treated with an emery buffing machine to form a nanofiber aggregate raised surface, and further dyed, Finished to obtain a suede-like artificial leather. The texture of this is simply a suede imitation and does not exceed the conventional artificial leather using ultra-fine fibers.
[0139]
(Example 27)
The polymer alloy fiber produced in Example 2 was subjected to mechanical crimping, then cut to a fiber length of 51 mm, defibrated with a card, and then made into a web with a cross wrap weber. Next, using a needle punch, the basis weight is 400 g / m. ² After the fiber entangled nonwoven fabric was made, it was subjected to an alkali treatment with a 3% aqueous sodium hydroxide solution (60 ° C., bath ratio 1: 100) for 2 hours to remove 99% or more of the copolymerized PET, and a basis weight of 200 g / m ² N6 nanofiber nonwoven fabric was obtained. The number average single fiber diameter of the obtained N6 nanofibers was 86 nm (6 × 10 6 ^-Four dtex), and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. A circular filter column was prepared by stacking 5 pieces of this cut into a 4.7 cm diameter circle, and bovine blood containing white blood cells (5700 / μl) was passed at a flow rate of 2 ml / min. The time required for the pressure loss to reach 100 mmHg was 100 minutes, and the granulocyte removal rate at that time was 99% or more, and the lymphocyte removal rate was 60%, and granulocytes, which are inflammatory leukocytes, could be selected. . This is considered to be an effect due to the gap between the nanofibers. Moreover, since the basis weight was sufficiently large, troubles such as filter breakage during the test did not occur.
[0140]
(Example 28)
When 0.5 g of nanofiber nonwoven fabric prepared in Example 27 was sterilized by autoclave and the adsorption ability was evaluated with bovine serum containing 15 ml of endotoxin (37 ° C., 2 hours), the endotoxin concentration LPS was 10.0 ng. / Ml and reduced to 1.5 ng / ml and showed excellent adsorption capacity. This is presumably because N6 nanofibers have much more active surfaces than normal nylon fibers, so that there are much more amino ends than usual.
[0141]
(Example 29)
A spunbonded nonwoven fabric was obtained with the same polymer combination as in Example 13 using the apparatus of FIG. That is, the yarn 7 was collided with the spread plate 26 through the ejector 25 to form a spread yarn 27, and was collected by the collecting device 28. At this time, the melting temperature in the biaxial extrusion kneader 23 was 225 ° C., the spinning temperature was 230 ° C., and the die surface temperature was 217 ° C. The base was the same as that used in Example 1, the single-hole discharge rate was 0.8 g / min, and the distance from the bottom of the base to the start of cooling was 12 cm. By treating the obtained polymer alloy nonwoven fabric with hot water at 60 ° C. for 2 hours, 99% or more of the hot water soluble polymer is dissolved and removed, and the basis weight of PLA nanofibers is 20 g / m. ² A non-woven fabric was obtained. The number average nanofiber single fiber diameter of this nonwoven fabric is 50 nm (2 × 10 ^-Five dtex), 98% or more of the fineness ratio is 1 × 10 ^-7 ~ 1x10 ^-Four In the range of dtex, the nanofiber single fiber diameter was in the range of 45 to 74 nm, and the fineness ratio was 70%. This PLA non-woven fabric was light, and when used, the non-woven fabric did not break and was suitable for wrapping.
[0142]
(Example 30)
The circular knitted fabric composed of the nanofiber assembly produced in Example 1 and Example 2 was placed in a 15% by weight aqueous solution of a polyurethane prepolymer (molecular weight 3000 to 4000) composed of hexamethylene diisocyanate and a molecular weight 1000 hexamethylene polycarbonate for 30 minutes. Soaked. Thereafter, the circular knitted fabric was pulled up to crosslink the polyurethane prepolymer at 120 ° C. for 20 minutes. By this operation, the polyurethane prepolymer that entered the voids between the nanofibers was insolubilized by the crosslinking reaction, and a composite composed of the crosslinked polyurethane and N6 nanofibers was generated. The obtained circular knitted fabric-shaped composite had a large stretch property and a good surface touch that was sticky. The ratio of N6 nanofibers in this composite was 50% by weight and 60% by weight, respectively.
[0143]
(Example 31)
The circular knitted fabric made of the nanofiber aggregate produced in Example 1 and Example 2 was immersed in ion-exchanged water, and then 1,2-bis (trimethoxysilyl) ethane was added and stirred for 3 hours. The mixture was allowed to stand at room temperature for 14 hours, further stirred for 13 hours, further allowed to stand at room temperature for 14 hours, and further stirred for 7 hours to polymerize silica. Thereafter, the circular knitted fabric was washed with ion-exchanged water and then air-dried. By this operation, a fabric-shaped N6 / silica composite using N6 nanofibers as a template was obtained. This was an excellent material having both sufficient rigidity and flexibility. It was also a hybrid material with excellent flame retardancy. The ratio of N6 nanofibers in this composite was 40 and 50% by weight, respectively.
(Example 32)
The knitted fabric composed of the polyester nanofiber aggregates produced in Examples 9 to 13 was exhausted with a trade name “SR1000” (10% aqueous dispersion) manufactured by Takamatsu Yushi Co., Ltd. as a hygroscopic agent. The processing conditions at this time were 20% owf as the solid content of the hygroscopic agent, a bath ratio of 1:20, a processing temperature of 130 ° C., and a processing time of 1 hour. The exhaust rate of this hygroscopic agent to normal polyester fibers is almost 0%, but the exhaust rate to this polyester nanofiber aggregate is 10% or more, and ΔMR = 4% or more, which is equal to or better than cotton. A polyester knitted fabric having high hygroscopicity could be obtained.
[0144]
(Example 33)
750 g / m per unit area produced in Example 26 ² The polymer alloy short fiber nonwoven fabric was immersed in a 3% sodium hydroxide aqueous solution (90 ° C., bath ratio 1:50) for 2 hours to remove 99% or more of the copolymerized PET, and from the N6 nanofiber aggregate. The basis weight 150 and 375 g / m ² A non-woven fabric was obtained. The number average diameters of N6 nanofibers were 60, 86, 61 and 61 nm, respectively. Then, methyltrimethoxysilane oligomer (n = 3 to 4) is dissolved in isopropyl alcohol / ethylene glycol = 1/1 mixed solution, and dibutyltin diacetate is used as a polymerization catalyst for the silicone polymer having a siloxane bond. A silicone polymer coating solution was prepared by adding wt%. A nonwoven fabric composed of N6 nanofiber aggregates was immersed in this at 30 ° C. for 20 minutes, and sufficiently impregnated with a coating solution. Then, the nonwoven fabric is pulled up from the coating solution, dried at 60 ° C. for 2 minutes, 80 ° C. for 2 minutes, and 100 ° C. for 2 minutes, and the silicone polymerization is advanced to obtain a nonwoven fabric in which N6 nanofibers are coated with the silicone polymer. It was. This was a nonwoven fabric exhibiting excellent water repellency and flame retardancy. The content of N6 nanofibers in this coated nonwoven fabric was 85% by weight.
[0145]
(Example 34)
The basis weight 150 and 375 g / m comprising the N6 nanofiber aggregate produced in Example 33 ² The non-woven fabric exhibited a water content of 160% or more by its own weight and a water retention of 80% or more of its own weight, and was excellent in water absorption and water retention. Here, the moisture content and the water retention rate were obtained by sufficiently immersing the sample in a water bath for 60 minutes, then pulling it up and measuring the weight (Ag) of the sample from which the water adhering to the surface was removed. The weight (Bg) of the dehydrated sample was measured, and the weight (Cg) of the sample dried at 105 ° C. for 2 hours was measured and calculated by the following formula.
Water content (%) = (A−C) / C × 100 (%)
Water retention rate (%) = (BC) / C × 100 (%)
Furthermore, the non-woven fabric composed of this N6 nanofiber aggregate exhibited specific adhesiveness particularly in a state containing 15% or more of water.
[0146]
(Example 35)
A poultice base fabric was produced using the nonwoven fabric made of the N6 nanofiber aggregate produced in Example 33. When a drug was applied to this, the exhaustion of the drug was good, and it showed excellent adhesiveness, and an excellent poultice material could be obtained. The content of N6 nanofibers in this patch material was 75% by weight.
[0147]
(Example 36)
Using a N6 / copolymerized PET alloy false twisted yarn produced in Example 3 as a ground structure, a tricot knitted fabric having a 100 dtex, 36 filament polybutylene terephthalate (PBT) yarn as a raised pile part, And knitting with a knitting density of 64 courses, and then immersed in a 3% aqueous sodium hydroxide solution (70 ° C., bath ratio 1: 100) for 1 hour to obtain 99 of copolymerized PET in polymer alloy fibers. % Or more was removed by hydrolysis to obtain a fabric for automobile interior. As a result, the basis weight of the obtained fabric for automobile interior is 130 g / m. ² The N6 nanofiber content was 40% by weight. The basis weight of the N6 nanofiber part is 120 g / m ² Met. Moreover, the single fiber diameter by the number average of nanofibers is 84 nm (6 × 10 ^-Five dtex) and unprecedented fineness, and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small. Then, this was immersed in a 3% aqueous solution of diethylenetriamine at 50 ° C. for 1 minute, thereby supporting diethylenetriamine on N6 nanofibers. When this acetaldehyde removal ability was evaluated, the concentration decreased from 30 ppm to 1 ppm in 10 minutes, and an excellent removal ability was shown.
[0148]
(Example 37)
N6 / copolymerized PET alloy polymer used in Example 2 and melt viscosity 2400 poise (262 ° C., shear rate 121.6 sec) ^-1 ), PBT having a melting point of 220 ° C. was melted separately, and sea-island composite spinning was performed in the same manner as in Example 2 using a die having 24 holes, a discharge hole diameter of 1.0 mm, and a discharge hole length of 1.0 mm. At this time, the sea component was alloy polymer, the island component was PBT, the island component composite ratio was 35% by weight, and the number of islands per hole was 36 islands. The spun yarn is taken up at 900 m / min, then stretched and heat-treated at a temperature of the first hot roller 17 of 85 ° C., a temperature of the second hot roller 18 of 130 ° C. and a draw ratio of 3.0 times, and 240 dtex, 24 A sea-island composite yarn having a filament, a strength of 3.0 cN / dtex, an elongation of 40%, and a polymer alloy of U% 2.0% as a sea and PBT as an island was obtained. Then, after applying a sweet twist of 300 turns / m to this, a 2/2 twill fabric was woven using the warp and the weft. Next, this woven fabric was immersed in a 3% aqueous sodium hydroxide solution (70 ° C., bath ratio 1: 100) to hydrolyze and remove 99% or more of the copolymerized PET in the polymer alloy fibers. As a result, the basis weight of 200 g / m consisting of a mixed yarn of N6 nanofibers and PBT superfine yarn (0.08 dtex) in which the weight ratio of N6 nanofibers to PBT is 55% by weight: 45% by weight. ² Fabric was obtained. Moreover, the single fiber diameter by the number average of N6 nanofiber is 84 nm (6 × 10 6 ^-Five dtex) and unprecedented fineness, and the single fiber fineness is 1 × 10 ^-7 ~ 1x10 ^-Four The fineness ratio of dtex was 78%, in particular, the single fiber fineness ratio falling between 75 and 104 nm in terms of single fiber diameter was 64%, and the single fiber fineness variation was very small.
[0149]
This fabric has N6 nanofibers opened due to electrostatic repulsion due to the difference in chargeability between N6 and PBT, and is super soft and super peachy without buffing or silicone treatment. Excellent texture with freshness. Furthermore, since the PBT supports the fabric skeleton, not only the dimensional stability is improved but also the rebound is excellent. A windbreaker was made using this fabric, but not only did the N6 nanofibers open, but also an excellent windproof property was exhibited, and there was no “gutter” sound even when moving violently in sports due to the super soft texture. In addition, since excellent hygroscopicity is exhibited by the N6 nanofibers, the wearing comfort is very excellent. Moreover, it was washed and dehydrated without putting it in a washing net with a household washing machine, but it did not lose its shape and showed good dimensional stability.
[0150]
【The invention's effect】
According to the present invention, it is possible to obtain a fiber structure including nanofibers as a material excellent in durability while having excellent moisture absorption / adsorption performance.
[0151]
In addition, the fiber structure containing the nanofibers of the present invention can not only improve the housing environment, but also textile products that can meet various needs of modern society, such as industrial materials and comfortable clothing fields with excellent characteristics. A fiber utilization product can be obtained.
[Brief description of the drawings]
1 is a TEM photograph showing a cross-section of an aggregate fiber of nylon nanofibers 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 SEM photograph showing the state of the fiber side surface of the nanofiber assembly of Example 1. FIG.
4 is an optical micrograph showing the state of the fiber side surface of the nanofiber assembly of Example 1. FIG.
FIG. 5 is a diagram showing a single yarn fineness variation of the nanofiber of Example 1.
FIG. 6 is a diagram showing a single yarn fineness variation of the nanofiber of Example 1.
FIG. 7 is a diagram showing a variation in single fiber fineness of the ultrafine yarn of Comparative Example 4.
FIG. 8 is a diagram showing a variation in single fiber fineness of the ultrafine yarn of Comparative Example 4.
FIG. 9 is a diagram showing a variation in single fiber fineness of the ultrafine yarn of Comparative Example 5.
FIG. 10 is a diagram showing a variation in the fiber yarn fineness of the super extra fine yarn of Comparative Example 5.
FIG. 11 is a schematic diagram showing an example of a spinning machine.
FIG. 12 is a side sectional view showing a base.
FIG. 13 is a schematic diagram showing an example of another stretching machine.
FIG. 14 is a schematic diagram showing an example of another spinning machine.
FIG. 15 is a schematic diagram showing an example of another spinning machine.
FIG. 16 is a schematic diagram showing an example of another spinning machine.
FIG. 17 is a schematic diagram showing an example of a spunbond spinning apparatus.
FIG. 18 is a schematic diagram showing an example of a false twisting device.
[Explanation of symbols]
1: Hopper
2: Melting part
3: Spin block
4: Spin pack
5: Cap
6: Chimney
7: Yarn
8: Focused lubrication guide
9: First take-up roller
10: Second take-up roller
11: Winding yarn
12: Measurement unit
13: Discharge hole length
14: Discharge hole diameter
15: Undrawn yarn
16: Feed roller
17: First hot roller
18: Second hot roller
19: Third roller (room temperature)
20: drawn yarn
21: 1-axis extrusion kneader
22: Static kneader
23: Biaxial extrusion kneader
24: Chip weighing device
25: Ejector
26: spread plate
27: Open yarn
28: Collection device
29: Raw yarn
30: Feed roller
31: Heater
32: Cooling plate
33: Rotor
34: Delivery roller
35: False twisted yarn

Claims (13)

A fiber structure comprising nanofibers comprising at least 10% by weight of nanofibers having the following characteristics made of an organic polymer and having a fiber basis weight of 20 to 2000 g / m ² .
Number average single fiber fineness = 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ dtex The fiber structure containing nanofibers according to claim 1, wherein 60% or more of the fineness ratio of the nanofibers is in a range of single fiber fineness of 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ dtex. The fiber structure containing nanofibers according to claim 1 or 2, wherein nanofibers having a fineness ratio of 50% or more fall within a width of 30 nm with a single fiber diameter difference. The fiber structure containing the nanofiber according to any one of claims 1 to 3, wherein the melting point of the nanofiber is 165 ° C or higher. The fiber structure containing nanofiber according to any one of claims 1 to 4, wherein the organic polymer is at least one polymer selected from the group consisting of polyester, polyamide and polyolefin. The fiber structure containing the nanofiber according to any one of claims 1 to 5, wherein the strength of the nanofiber is 1 cN / dtex or more. The fiber structure containing the nanofiber according to any one of claims 1 to 6, wherein the moisture absorption rate of the nanofiber is 4% or more. The fiber structure containing nanofibers according to claim 1, which is obtained by dissolving and removing a sea polymer from a fiber structure composed of polymer alloy fibers having an island polymer blend ratio of 20 to 60% by weight. The fiber product which consists of a fiber structure containing the nanofiber of any one of Claims 1-8 . Fiber basis weight is 25 to 40 g / m ² The textile product according to claim 9, which is a non-woven fabric for packaging. Fiber basis weight is 50 to 200 g / m ² The textile product according to claim 9, which is a textile product for clothing. Fiber basis weight is 100 to 250 g / m ² The textile product according to claim 9, which is a curtain. Fiber basis weight is 100 to 350 g / m ² The fiber product according to claim 9, which is a car seat.

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