JP4130035B2 - Multi-divided hollow polyester fiber and woven / knitted fabric, artificial leather and nonwoven fabric using the fiber - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、機械的応力を作用させることにより容易に分割させることのできる多分割性中空繊維、並びに該繊維を使用し、加工工程において分割させてなる保温性及び風合に優れた織編物、ソフトな風合を呈する人工皮革及び不織布に関するものである。
【０００２】
【従来の技術】
従来、極細繊維は市場の要求が強く、その製造方法及び用途開発については数多くの提案がなされている。
【０００３】
例えば、孔径の小さな紡糸口金を用いて、吐出されたポリマーを高速紡糸することにより細い未延伸糸を作成し、次いで高倍率延伸して極細繊維とする方法が提案されている。しかし、このような方法では単繊維繊度は０．３デニール程度が限界であり、これより細い極細繊維を製造することは技術的に困難である上、例え可能であっても生産性が著しく低下するためにコストが増大するという問題がある。
【０００４】
また別の方法として、互いに非相溶な２種類のポリマーを混合紡糸した後、一方の成分を溶出除去する方法（特公昭４２−１９５１８号公報）が提案されているが、かかる方法では互いに非相溶なポリマーの接触面が剥離し易いためにカード通過性が不十分であり、また得られる繊維の繊度は小さくなりやすく、且つ繊維長もランダムで短いため、用途によっては使用できないという問題がある。
【０００５】
また、互いに非相溶な２種類のポリマーを海島状又は放射状もしくは層状の交互積層構造に複合紡糸した後、一方の成分を溶出除去する方法（特公昭４７−３０７２３号公報、特開平４−１５３３２１号公報など）も提案されている。この方法によれば、適度な繊度で繊維長も長い（フィラメント状）極細化繊維が得られるが、海成分を溶出除去する必要上、生産性が低いだけでなく溶出工程も複雑でコストが高いものになるという問題がある。
【０００６】
さらに別の方法として、２種以上のポリマーを放射状又は層状に交互積層した複合繊維を、熱膨張・収縮特性の差や、機械的衝撃力により分割させる方法（特開昭６２−１３３１６４号公報）が提案されている。しかし、かかる方法では分割性が劣るだけでなく、複数のポリマーを使用する必要があり、また生産設備も複雑になって生産性が低下するという問題がある。
【０００７】
さらに、ポリマー中に適当な添加剤を入れて中空繊維となした後、アルカリ減量処理などを施すことにより、中空部が形成されるときに接合したポリマー間を剥離させる方法（特開平８−３２５９４５号公報、特開平８−２６０３４３号公報）が提案されているが、かかる方法では分割部が用いる中空ノズル孔の接合部に限定されるため、多分割させて極細繊維となすには限界がある。また、アルカリ減量処理が必要なので、用途が限定されるという問題もある。
【０００８】
この様に、従来提案されている分割方式又は一方成分の溶出方式による極細繊維化方法では、幅広い分野で使用可能な極細繊維を効率よく生産することができないというのが実状である。
【０００９】
【発明が解決しようとする課題】
本発明は、上記従来技術の有する問題を鑑みなされたもので、その目的は、カード工程等の繊維製品製造時にはその取扱性に優れると共に、機械的応力によって容易に分割して極細繊維化することができる多分割性中空ポリエステル繊維を提供することにある。
【００１０】
また本発明の別の目的は、保温性や風合に優れた織編物、ソフトな風合の人工皮革、及びソフトな風合の抄紙や詰物などの不織布を提供することにある。
【００１１】
【課題を解決するための手段】
本発明者らの研究によれば、前記本発明の目的は、スルホン酸塩基を有する共重合成分が全酸成分に対して１〜６モル％共重合された固有粘度が０．３５〜０．７０であるエチレンテレフタレート系ポリエステルからなる中空ポリエステル繊維において、該繊維の繊度が０．５〜８．０デニール、中空率が２５％以上、結晶化度が２０％以上、（０１０）面の結晶サイズが４ｎｍ以上であり、且つ該中空繊維には、その繊維軸方向に配列した複数の不連続分割孔が存在することを特徴とする多分割性中空ポリエステル繊維により達成されることが見出だされた。
【００１２】
また、本発明者らの研究によれば、前記本発明の他の目的は、
▲１▼ 織編物の構成繊維の少なくとも２０重量％が、上記の多分割性中空ポリエステル繊維を分割してなる極細繊維である保温性及び風合に優れた織編物、
▲２▼ 人工皮革の構成繊維の少なくとも２０重量％が、上記の多分割性中空ポリエステル繊維を分割してなる極細繊維である風合に優れた人工皮革物、
▲３▼ 不織布の構成繊維の少なくとも３０重量％が、上記の多分割性中空ポリエステル繊維を分割してなる極細繊維であるソフトな風合いを有する不織布、
により達成されることが見出された。
【００１３】
【発明の実施の形態】
以下、本発明について詳細に述べる。
本発明の中空ポリエステル繊維は、エチレンテレフタレートを主たる繰返し単位とし、スルホン酸塩基を有する共重合成分が全酸成分を基準として１〜６モル％、好ましくは２〜５モル％共重合されたエチレンテレフタレート系コポリエステルからなることが大切である。スルホン酸塩基を有する共重合成分の量が１モル％未満の場合には、繊維軸方向に配列した分割孔を中空壁に形成することが困難になり、機械的応力を作用させても中空壁の分割が起りがたく、極細繊維化することができなくなる。一方、該共重合成分の量が６モル％を越える場合には、繊維軸方向に配列した分割孔を中空壁に形成することは可能であるものの、製糸時の工程安定性が低下するので好ましくない。
【００１４】
好ましく用いられるスルホン酸塩基を有する共重合成分としては、５−ナトリウムスルホイソフタル酸、５−カリウムスルホイソフタル酸、５−リチウムスルホイソフタル酸、４−ナトリウムスルホイソフタル酸、４−ナトリウムスルホ−２，６−ナフタレンジカルボン酸、及びこれらのエステル形成性誘導体をあげることができ、これらは単独でも２種以上を併用してもよい。
【００１５】
この様な本発明にかかるポリエステルには、本発明の目的を損なわない範囲内で上記以外の共重合成分を共重合してもよく、通常その割合は全酸成分を基準として１０モル％以下である。共重合し得る成分としては、例えば酸成分としてイソフタル酸、ジフェニルジカルボン酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸、コハク酸、アジピン酸、セバチン酸等の脂肪族ジカルボン酸、パラヒドロキシ安息香酸、４−（β−ヒドロキシエトキシ）安息香酸等のオキシカルボン酸があげられ、またジオール成分としては、１，３−プロパンジオール、１，６−へキサンジオール、ネオペンチルグリコール等の脂肪族ジオール、１，４−ビス（β−ヒドロキシエトキシ）ベンゼン等の芳香族ジオール、ポリエチレチングリコール、ポリブチレングリコール等のポリアルキレングリコール等があげられる。なおこれらの成分は、単独で共重合させても２種以上を同時に共重合させてもよい。
【００１６】
上記ポリエステルの重合度（固有粘度）は、大きくなりすぎると紡糸時の工程安定性が低下して細繊度のものが得難くなる傾向にあり、一方小さくなりすぎると高中空のものが得難くなる傾向にあるので、オルソクロロフェノール中３５℃で測定した固有粘度（ＩＶ）で０．３５〜０．７０、好ましくは０．４０〜０．５５の範囲が適当である。
【００１７】
また、上記ポリエステルには各種添加剤を混合してもよく、例えば抗菌剤、親水剤、防ダニ剤、消臭剤、遠赤外線放射性剤等の各種機能性付与剤、二酸化チタン、酸化ケイ素、酸化亜鉛、硫酸バリウム、酸化ジルコニウム、酸化アルミニュウム、酸化マグネシウム、酸化カルシウム、トルマリン等の無機微粒子をあげることができ、目的に応じて適宜選択使用すればよい。ただし、無機微粒子を配合する際には、ポリエステル中への分散性の点から、その平均粒径は１．０μｍ以下、好ましくは、０．１〜０．７μｍが適当であり、また、その混合量は１〜１０重量％、特に２〜７重量％の範囲が適当である。
【００１８】
上記のポリエステルからなる本発明の多分割性中空ポリエステル繊維は、その単繊維繊度が０．５〜８．０デニール、好ましくは１．０〜４．０デニール、特に好ましくは１．５〜３．０デニールの範囲にあることが必要である。単繊維繊度が０．５デニール未満の場合には、安定に生産することができなくなり、また得られる繊維の中空率も小さくなりやすいため好ましくない。一方８．０デニールを越える場合には、製糸時の工程安定性は良好であるが、繊維横断面における中空壁面の厚さが大きくなるため、繊維軸方向に配列した分割孔は形成され難くなり、機械的応力を作用させても極細繊維に分割できなくなるので好ましくない。
【００１９】
次に繊維横断面における中空率は２５％以上、好ましくは４０〜６０％の範囲にあることが必要である。中空率が２５％未満では、機械的応力を作用させても極細繊維に分割できなくなるので好ましくない。一方、中空率が大きくなると中空壁面の厚さが薄くなり、中空破断が発生して製糸の工程安定性が低下したり、得られる繊維の機械的特性が低下するので、８５％以下が望ましい。なお、ここでいう中空率とは、繊維横断面において該横断面の外周部で囲まれた面積に対する、中空部の面積の割合（％）をいう。
【００２０】
中空部の繊維横断面における位置は、繊維横断面の中心が望ましく、偏心が大きくなると均一に分割しにくくなり、ソフトな風合を得ることが困難になる。
【００２１】
また、中空部を構成する壁面の厚さは５μｍ以下、特に１．０〜３．０μｍの範囲にある場合、優れた分割極細化の性能を示す。一方壁面の厚さが薄くなりすぎると製糸し難くなり、また後加工工程において断糸が発生したり耐摩耗性が低下する場合がある。
【００２２】
本発明の多分割性中空ポリエステル繊維においては、上記の特性に加えて、広角Ｘ線回折写真から計算される結晶化度が２０％以上、特に２２〜３３％の範囲にあること、及び広角Ｘ線回折写真の（０１０）面回折ピークの半値幅から計算される結晶サイズが４．０ｎｍ以上、好ましくは５．０〜８．５ｎｍの範囲にあることが、良好な多分割性能を示すために肝要である。結晶化度が２０％未満又は（０１０）面の結晶サイズが４．０ｎｍ未満の場合には、分割性が低下して極細繊維化が困難になるので好ましくない。
【００２３】
本発明の多分割性中空ポリエステル繊維は、さらにその中空壁に、繊維軸方向に配列した複数の不連続分割孔が存在している必要がある。なおここでいう不連続分割孔とは、繊維軸方向には長さが有限で、繊維表面から中空部まで貫通又は未貫通の孔（スリット状、クラック状等）である。この様な分割孔が存在しない場合には、機械的応力による分割極細化が進行しなくなるので好ましくない。
【００２４】
以上に説明した本発明の多分割性中空ポリエステル繊維は、繊維軸方向の機械的特性は良好であるが、繊維軸に垂直な方向の特性は劣っているので、機械的応力を作用させることにより、繊維の９０％以上が４個以上、好ましくは５〜２０個に分割されて極細繊維化することができる。まお、分割処理に先立って１００℃以上の温度で緊張熱処理を施すと、分割が容易になるので好ましい。
【００２５】
なお、本発明の多分割性中空ポリエステル繊維は短繊維であっても長繊維であってもよく、使用目的及び用途に応じて適宜設定すればよい。
【００２６】
以上に述べた本発明の多分割性中空ポリエステル繊維は、例えば、前記ポリエステルを、以下に述べるような特殊な溶融紡糸方法によって製造することができる。すなわち、溶融ポリエステルを複数のスリット孔からなる中空糸製造用紡糸孔を具備する紡糸口金から吐出し、紡糸口金直下０〜５０ｍｍの間で、該吐出糸条に温度１５０〜２３０℃、好ましくは１８０〜２１０℃の加熱気体を吹き付ける。吹き付け角度は吐出糸条走行方向に垂直な方向から３０〜４５度の角度で口金面に向けるようにする（したがって、糸条の走行方向と相向するように吹き付ける）。吹き付け速度は１．０〜５．０ｍ／秒、好ましくは２．０〜３．０ｍ／秒である。
【００２７】
加熱ゾーンを通過した糸条は、長さ５０〜１５０ｍｍの緩衝ゾーンを通過させた後に冷却固化させる。冷却固化するには、冷却風温度を１５〜３５℃、好ましくは２０〜２５℃とし、該冷却風速度を０．２〜４．０ｍ／秒、好ましくは１．５〜３．５ｍ／秒とする。糸条の冷却範囲は１００〜４５０ｍｍ、好ましくは１５０〜３５０ｍｍの範囲が適当であり、これを外れると得られる繊維の品質が低下するので好ましくない。
【００２８】
次に冷却固化した糸条は、紡糸ドラフトが１５０以上、好ましくは１５０〜５００、特に好ましくは２００〜４００で、且つ引取速度が５００〜２０００ｍ／分、好ましくは１０００〜１８００ｍ／分で引取る。紡糸ドラフトが１５０未満になると紡糸安定性が低下すると同時に、繊維微細構造における（０１０）面の結晶サイズも小さくなるため好ましくない。さらに引取速度が２０００ｍ／分を越えると、繊維微細構造における（０１０）面の結晶サイズは大きくなるが、中空率２５％以上でかつ結晶サイズ及び結晶化度を同時に満足するものは得られなくなり、一方５００ｍ／分未満では（０１０）面の結晶サイズが小さくなるので好ましくない。なお、紡糸ドラフトがあまりに大きくなりすぎると、引続いて延伸する場合の延伸性が低下する傾向にあるので前記のように５００以下にするのが望ましい。
【００２９】
この様にして引取られた未延伸糸は、最終的な用途に応じて延伸され、次いで適宜熱処理される。例えば、温度５０〜７０℃の温水中で、２．０〜５．０倍の延伸倍率で延伸し、これを熱セットしない場合には高収縮タイプの中空繊維が得られ、加熱ローラーや熱プレート等で緊張熱処理すれば低収縮タイプの中空繊維が得られ、また一旦延伸処理した後、温水中等でオーバーフィードしながら熱処理すれば自己伸長タイプの中空繊維が得られる。この延伸時、前記のような特有な繊維微細構造を有しているため、一部が繊維表面から中空内部まで貫通する、繊維軸方向に配列したクラックが不連続に多数形成されるのである。
【００３０】
以上、本発明の多分割性中空ポリエステル繊維の製造法の一例について述べたが、本発明の多分割性中空ポリエステル繊維は、上記方法により製造されたものに限定されるものではなく、これとは異なる他の方法で製造したものであっても構わない。
【００３１】
この様にして得られる中空ポリエステル繊維は、繊維軸方向の機械的特性は良好である一方、繊維軸に垂直な方向の特性は劣っている。このため、機械的応力を作用させることによって、繊維軸方向に容易にクラックを発生して４０％以上の繊維を分割極細繊維化できる。この際、例えば予め緊張熱処理を施しておくと、さらに分割性が向上して９０％以上の繊維が４個以上の極細繊維に容易に分割できるのである。
【００３２】
以上に述べた本発明の多分割性中空ポリエステル繊維は、１００％で用いられたりあるいは他の繊維（本発明外のポリエステル繊維等の合成繊維、綿やウール等の天然繊維）と混合使用されて、分割極細繊維化に基づく各種優れた特性を有する繊維製品を得ることができる。
【００３３】
例えば、本発明の多分割性中空ポリエステル繊維を、織編物構成繊維の２０重量％以上、好ましくは３０重量％以上占めるようにすることにより、織編物を製造する工程で該多分割性中空繊維の分割極細繊維化が起こり、保温性に優れ、且つソフトな風合を呈する織編物を得ることができる。
【００３４】
また、本発明の多分割性中空ポリエステル繊維を、人工皮革構成繊維の２０重量％以上、好ましくは３０重量％以上占めるようにすることにより、人工皮革の製造工程で該多分割性中空繊維の分割極細繊維化が起こり、ソフトタッチな風合を呈し、しかも軽量性に富んだ人工皮革を得ることができる。
【００３５】
また不織布にする場合、本発明の繊維を不織布構成繊維の３０重量％以上、好ましくは４０重量％以上、特に好ましくは５０重量％以上占めるようにすることにより、目付を小さくしても保温性に優れ、しかもソフトな風合を呈する不織布が得られる。なお、抄紙法による湿式不織布の場合には、繊維長３〜３０ｍｍのショートカット繊維とし、これを従来公知の叩解機（例えば、ディスクリファイナー）を用いて叩解することにより、予め多分割されたフィブリッド状繊維を得る。この際、叩解機の運転条件は、使用する機械に対応させて最適な条件を選定すればよい。次いで、多分割性ポリエステル中空繊維より得られた該フィブリッド状繊維が水中に分散したスラリーに、抄紙用バインダーを添加した後、通常の抄紙機（長網式抄紙機、短網式抄紙機、円網式抄紙機など）を用いて抄紙し、ヤンキードライヤーで加熱乾燥することにより、従来にない均一で風合の柔らかい湿式不織布を得ることができる。なお、抄紙工程において発泡や分散が不十分な場合などには、通常用いられている分散剤、粘剤などといった抄紙用助剤を用いても何ら問題はない。
【００３６】
ここで用いられる抄紙用バインダーとは、抄紙時に通常用いられる水溶性の粘着物質であって、例えばゼラチン、アルギン酸ソーダ等の天然水溶性高分子、リン酸化デンプン、シアノエチル化デンプン、カルボキシメチルセルロース、ヒドロキシプロピルメチルセルローズ等の半合成水溶性高分子、ポリビニルアルコール、ポリアクリル酸ソーダ、ポリアクリルアミド等の合成水溶性高分子、及びポリエチレンオキサイド、ポリリン酸塩等を例示することができ、これらは単独又は混合して使用することができる。また、塩化ビニル、酢酸ビニル、スチレン、アクリロニトリル、アクリル酸エステル、ブタジエン、エチレンなどの単一もしくは共重合体からなる合成ラテックスに、可塑剤や各種の安定剤等を加えたものも使用することができる。
【００３７】
また、該抄紙用バインダーは繊維状であってもよく、例えばポリビニールアルコ−ル繊維、ポリエチレンオキサイド繊維等の、抄紙後の湿熱条件下でバインダー性能を発揮する繊維を使用することができる。さらに、ポリプロピレン、クロルスルホン化ポリエチレン、エチレン酢酸ビニル共重合体のように、通常抄紙後に施される８０〜１７０℃の熱処理によって融着し、接着効果を発現する成分の単独繊維、又はこれらのポリマーとこれらのポリマーより融点が２０℃以上高い他のポリマーとのサイドバイサイド型もしくはシースコア型に複合された熱接着性複合繊維を用いることもできる。
【００３８】
上記フィブリッド状繊維は、湿式不織布全重量に対して３０重量％使用することが、得られる湿式不織布の風合(柔軟性)の観点から必要である。一方、上記に示したような抄紙用バインダーは、同じく全重量に対して５〜３０重量％の範囲が適当である。バインダー量が上記範囲未満の場合には、湿式不織布としての強力が不足して取扱いが困難になる。逆に上記範囲を超える場合には、繊維間の固着点が多くなって、フィブリッド状繊維によるソフトな風合の発現が不十分なものとなりやすい。上記フィブリッド状繊維及びバインダー以外には、例えば天然パルプ、合成パルプ、ポリエチレンテレフタレート繊維等を併用することが可能である。このように第3成分を混合すれば、さらに特徴のある湿式不織布を得ることが可能となる。
【００３９】
本発明の多分割性中空ポリエステル繊維は、１００％で使用してもあるいは他の繊維（本発明外のポリエステル繊維等の合成繊維、綿やウール等の天然繊維）と混合して使用しても、分割極細繊維化を何等問題なく起こさせることができるので、上記の特性を発揮するが、その他にも各種優れた特性を有する。例えば、極細繊維をカードにかける場合にはカード通過性が著しく低下するが、本発明の多分割性中空ポリエステル繊維の場合、先ず繊維軸方向に不連続な分割が起こるのみであるため、分割された個々の極細繊維は当初集合体状でバラバラになることはなく、極細繊維集合体として挙動する。このため、カード通過性が向上するのである。
【００４０】
【実施例】
以下、実施例により本発明をさらに具体的に説明するが、本発明は何等これらに限定されるものではない。なお、実施例中における各特性値の測定は、以下の方法にしたがった。
【００４１】
＜固有粘度＞
オルソクロルフェノールを溶媒として、３５℃で測定した。
＜繊度＞
ＪＩＳ−Ｌ１０１５ ７−５−１Ａ法により測定した。
＜中空率＞
画像解析システム、ピアスー２（ピアス（株）製）を用いて単繊維のセクション断面画像を５００倍に拡大し、単繊維の断面積（中空部を含む）と中空部面積を測定してその面積比より求めた。
【００４２】
＜分割孔＞
繊維の側面拡大写真から、繊維軸方向に配列した複数の不連続分割孔の有無を判定した。
＜中空壁面厚さ＞
上記の５００倍断面画像から単繊維の断面積（中空部を含む）と中空部面積を測定し、その中空壁面厚さを計算により求め、ｎ＝２０の平均値で示した。
＜繊維の分割割合＞
製品の断面写真を撮り、写真から単糸を５０本ランダムに選択し、中空壁が４か所以上で分割している割合を求めた。
＜中空繊維の平均中空分割数＞
上記の断面写真から単糸を１０本ランダムに選択し、各中空繊維が分割している個数を測定し、平均値を求めた。
【００４３】
＜結晶化度＞
広角Ｘ線回折像から定法にしたがって求めた。
＜（０１０）面結晶サイズ＞
広角Ｘ線回折像の（０１０）面回折ピーク半価幅から、定法にしたがって求めた。
【００４４】
＜紡糸性及び延伸性＞
紡糸性は下記基準で評価した。
良好（○）：断糸回数＜０．１回／錘・日、密着糸＜０．１ヶ／錘・日
やや不良(△)：断糸回数が０．１〜０．２回／錘・日で密着糸が０．１〜０．２ヶ／錘・日
不良（×）：断糸回数＞０．２回／錘・日、密着糸＞０．２ヶ／錘・日
但し、ここでいう密着糸とは、単糸が２本以上が融着しているものをいう。
【００４５】
また延伸性は下記判定基準で評価した。
良好（○）：単糸切れによるローラー巻付き＜１回／台・日、未延伸糸の発生本数＜５本／１０万本
やや不良（△）：単糸切れによるローラー巻付きが１〜３回／台・日、未延伸糸の発生本数が５〜１０本／１０万本
不良（×）：単糸切れによるローラー巻付き＞３回／台・日、未延伸の発生本数＞１０本／１０万本
【００４６】
＜保温性＞
ＪＩＳ Ａ １４１２に準じて熱伝導率を測定し、熱伝導率の低い保温性に優れている物（熱伝導率が０．０４８ｋｃａｌ／ｍ・ｈ・ｄｅｇ以下）をＡランク、良い物（熱伝導率が０．０４８〜０．０５５ｋｃａｌ／ｍ・ｈ・ｄｅｇ）をＢランク、普通の物（熱伝導率が０．０５５〜０．０６０ｋｃａｌ／ｍ・ｈ・ｄｅｇ）をＣランク、劣っている物（熱伝導率が０．０６０ｋｃａｌ／ｍ・ｈ・ｄｅｇ超）をＤランクとして、ランク付けで判定した。
【００４７】
＜織物の軽量性＞
同じ目付の基布（面積５ｃｍ2）を５枚重ね、基布の厚みを測定して体積を算出し、軽量性を、繊度が１．５ｄｅ、中空率が３０％の通常の中空繊維使いを標準として相対比較により判定した。軽量性に優れている物をＡランク、良い物をＢランク、普通の物をＣランク、劣っている物をＤランクとして、ランク付けで判定した。
【００４８】
＜織編物、不織布等のソフトタッチ感、清涼感、ドレープ性、底付き感＞
手触り感にて官能評価し、優れている物をＡランク、良い物をＢランク、普通の物をＣランク、劣っている物をＤランクとして、ランク付けで判定した。
【００４９】
＜不織布初期嵩＞
ＪＩＳ−Ｌ１０９７比容積（初期嵩高性）法にしたがった。
まず原綿をカードに掛けて、試験片２０ｃｍ×２０ｃｍの大きさで質量（ｗ）が約４０ｇのウェブを作成し、これを１時間放置する。次にこの試験片に０．５ｇ／ｃｍ2の荷重板（大きさ：２０ｃｍ×２０ｃｍ）を載せ、さらに重り（Ａ）２Ｋｇを載せて３０秒間放置し、次いで重り（Ａ）を除いて３０秒間放置する。この操作を３回繰り返し、重り（Ａ）を除いて３０秒間放置後の荷重板の４隅の高さを測定し、その平均値（ｈ0ｍｍ）を求めて下記式より初期嵩を算出する。
初期嵩（ｃｍ3／ｇ）＝（２０×２０×ｈ0／１０）／ｗ
【００５０】
＜不織布初圧嵩＞
ＪＩＳ−Ｌ−１０９７比容積（圧嵩性）法にしたがって測定した。
まず、不織布初期嵩測定時の試験片に、０．５ｇ／ｃｍ2の荷重板（大きさ：２０ｃｍ×２０ｃｍ）を載せ、さらに重り（Ｂ）４ｋｇを３０秒間載た後、厚板の４隅の高さ測定してその平均値（ｈ1ｍｍ）を求め、下記式より比容績（初圧嵩性）を算出する。
初圧嵩（ｃｍ3／ｇ）＝（２０×２０×ｈ1／１０）／ｗ
【００５１】
＜曲げ硬さ＞
幅２．５ｃｍ×長さ９ｃｍの試験片を、端部から２ｃｍの位置で把持し、他方の端部から２ｃｍの位置を支点として曲げてゆき、試験片を最初に把持固定した時の試料方向から９０°曲げた時の反発力を歪み計（デジタルホースゲージ）で測定し、その反発力を試験片１ｃｍ幅の値に換算して示す。
【００５２】
＜カード通過性＞
原綿２ｋｇをフラットカードに、カード速度５０ｍ／分で通過させ、下記基準で評価した。
◎：カード詰まり、ウェブ切れ、ネップが発生せず、カード通過性が良好
○：カード詰まり、ウェブ切れはないが、若干のネップ発生が認められる
△：カード詰まりはないが、ウェブ切れ、ネップ発生が若干認められる
×：カード詰まり、ウェブ切れ、ネップ等の発生が認められる
【００５３】
＜紡績性＞
紡績工程（カード、梳毛、粗紡、精紡）の通過状態により、下記基準で評価した。
◎：全行程で特に問題なく通過
○：カード、梳毛、粗紡工程まで問題なく通過
△：カード、梳毛工程まで問題なく通過
×：カード工程だけ通過
【００５４】
＜曲げ剛性（ｋｇ／ｃｍ2）＞
６０×曲げ硬さ（ｇ／ｃｍ）／［試験片厚さ（ｍｍ）］3
＜座屈性＞
２０ｃｍ×２０ｃｍの試験片を曲率半径５ｍｍ程度に折り曲げ、該折曲部を指先でつかみながら漸次折曲部を移動させ、折曲部の丸味状態を観察する。
丸味が有って角のない場合を良、角が発生する物を不良とし、次の４段階：優れている物；◎、良い物；○、普通の物；△、劣る物；×に区分して評価した。
【００５５】
＜レザーライク性＞
幅２．５ｃｍ×長さ９ｃｍの試験片を２つに折り、試験片厚さの３倍まで折り曲げ圧縮した時の反発力を歪計で測定し、幅１ｃｍ当りの値（ｇ／ｃｍ）で表した。この値が大きいほどレザーライク性に優れていることを表す。
【００５６】
＜屈曲耐久性＞
ＪＩＳ−Ｋ−６５０５−５２５により測定した。
【００５７】
＜裂断長＞
ＪＩＳ−Ｐ−８１１３（紙及び板紙の引張り強さ試験方法）にしたがって測定した。
【００５８】
＜引裂き＞
ＪＩＳ−Ｌ−１０９６（一般織物試験方法）に記載の引裂き強さにしたがって測定した。
【００５９】
［実施例１］
酸化チタン含有量が０．０７重量％で、固有粘度が０．４５、５−ナトリウムスルホイソフタル酸成分（ＳＩＰ）の共重合量が４．５モル％であるポリエチレンテレフタレート系共重合ポリエステルを、中空型ノズルを２０００ホール有する紡糸口金から、ポリマー温度２６８℃、吐出量１６００ｇ／分で押出し、紡糸速度１８００ｍ／分で引取って単繊維繊度が４．０デニール、中空率が５０％の未延伸糸を得た。
【００６０】
この時、中空型ノズル（８個のスリット孔）の直下０〜５０ｍｍにわたって、温度２００℃、風速３．５ｍ／秒の熱風を吹付け角度３５度で吹付け、長さ１００ｍｍの緩衝ゾーンを通過させた後、温度２５℃風速３．５ｍ／秒の冷却風を長さ２５０ｍｍにわたって吹付けた。
【００６１】
得られた中空未延伸糸を、温度６５℃、延伸倍率２．８０倍で温水１段延伸し、１４０℃の加熱ローラーで緊張熱処理し、引続き、これに１２個／２５ｍｍの機械捲縮を付与してから１２０℃の熱風で熱セット後、所定の長さに切断して短繊維とした。得られた中空ポリエステル短繊維は繊度が１．５デニール、中空率が５０％であり、表面には繊維軸方向に配列した複数の不連続分割孔が存在していた。得られた繊維の評価結果を表１に示す。
【００６２】
［実施例２〜３、比較例１〜５］
実施例１において、ＳＩＰの共重合量及び固有粘度を表１のとおり変更し、また加熱及び冷却条件を表１のとおりにした以外は実施例１と同様にして未延伸糸を得た。
この未延伸糸を表１に記載の条件で延伸熱処理し、実施例１と同様に捲縮付与後切断して短繊維を得た。これらの評価結果を表１に合わせて示す。
【００６３】
【表１】
［実施例４〜７、比較例６〜７］
表２記載の特性を有する中空ポリエステル短繊維（繊維長３８〜１００ｍｍ）をリング紡績法によって撚数１７．１回／２５ｍｍ、英式綿番手３０の紡績糸を作成した。この紡績糸を製織して、織密度（経８７本／２５ｍｍ、緯６８本／２５ｍｍ）、幅１２７ｍｍの平織物とし、常法により精練した後に分散染料で染色した。なお、実施例７は、綿（コットン）と混合したものである。得られた織物特性を表２に合わせて示す。
【００６５】
【表２】
［実施例８〜１０、比較例８〜９］
表３記載の特性を有する、高収縮タイプと自己伸長タイプの中空ポリエステル短繊維（繊維長３８〜６４ｍｍ）を表３記載の割合で混合し、カードにかけてウェブとなし、次いで４０番レギュラーバーブを１つ有する針を装着したニードルロッカールームで８００本／ｃｍ2の打込み密度でパンチングを行って目付１５７ｇ／ｃｍ2の不織布を得た。この不織布を６８℃の温水中に２分間浸漬して面積収縮率で３５％収縮させた。次いで真空脱水した後、５０℃で５分間乾燥して目付２４２ｇ／ｃｍ2の不織布を得た。この不織布を１８０℃で、各々６０秒間加熱金属ドラムと６０メッシュのステンレスネットベルト間に保持して厚さ１．２ｍｍ、見掛密度０．２０２ｇ／ｃｍ3の不織布となし、次いで該不織布にポリウレタン樹脂の１２％ジメチルホルムアミド溶液にポリウレタン樹脂１００部に対してカーボンブラックを５部添加したもの（クリスボンＭＰ−１８５：大日本インキ化学（株）製）を平均に含浸せしめ、スクイズロールで絞った後に４０℃の温水中に浸漬して凝固させ、さらに溶媒が殆ど無くなるまで洗浄した後乾燥して人工皮革を得た。結果を表３に合わせて示す。
【００６７】
【表３】
［実施例１１〜１５、比較例１０〜１１］
表４記載の特性を有する中空ポリエステル短繊維（繊維長５１ｍｍ）をカードにかけてウエブとなし、目付６０ｇ／ｍ2の不織布とした。結果を表４に合わせて示す。
【００６９】
【表４】
［実施例１６〜１９、比較例１２〜１３］
実施例１における、捲縮を付与していない多分割性中空ポリエステル繊維（繊度１．５ｄｅ、繊維長５ｍｍ、中空率５０％、結晶化度３０％、結晶サイズ８．５ｎｍ、不連続分割孔あり）を、ディスクリファイナー（浴比１：１００（繊維と水の重量比））により多分割させた。この多分割された繊維の水スラリーに、バインダーとして熱融着温度が約１２０℃であるテレフタル酸／イソフタル酸／エチレングリコール／ジエチレングリコール共重合ポリエステルとポリブチレンテレフタレートとからなるサイド・バイ・サイド型複合繊維（繊度１．５ｄｅ、繊維長５ｍｍ、捲縮数ゼロ）、第３成分（フィブリッド繊維と同様に主体繊維）として通常のポリエステル繊維（繊度０．５ｄｅ、繊維長５ｍｍ、捲縮ゼロ）を表５記載のとおり混合し、目付が約５０ｇ／ｍ2となるように手抄きを行ない、ヤンキードライヤーにより乾燥、熱融着を行なって湿式不織布を得た。結果を表５に合わせて示す。
【００７１】
【表５】
【発明の効果】
以上に詳述した本発明の多分割性中空ポリエステル繊維は、機械的応力により繊維軸方向に容易にクラックが発生して分割極細繊維化させることができるので、例えば織編物に用いると、保温性に優れ且つソフトな風合を呈する織編物が得られる。また人工皮革の基布に用いると、極細繊維化によるソフトな風合に加えて、軽量性にも富んだ人工皮革製品が得られる。さらに不織布に用いると、分割極細繊維化による軽量保温効果に加えてソフトな風合を有する不織布が得られ、特に抄紙された紙（湿式不織布）の場合では目付が小さくても地合（目面）が良好であるという特徴をも有する。
【図面の簡単な説明】
【図１】本発明の多分割性中空ポリエステル繊維の断面の一例を示す。
【図２】本発明の多分割性中空ポリエステル繊維の側面の一例を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention is a multi-splitting hollow fiber that can be easily split by applying mechanical stress, and a woven or knitted fabric excellent in heat retention and feel formed by using the fiber and splitting in a processing step, The present invention relates to artificial leather and non-woven fabric having a soft texture.
[0002]
[Prior art]
Conventionally, there has been a strong market demand for ultrafine fibers, and many proposals have been made for the production method and application development.
[0003]
For example, a method has been proposed in which a thin undrawn yarn is prepared by spinning a discharged polymer at a high speed using a spinneret having a small pore diameter, and then drawn to a high fineness by drawing at a high magnification. However, in such a method, the limit of the single fiber fineness is about 0.3 denier, and it is technically difficult to produce finer fine fibers than this, and even if possible, the productivity is significantly reduced. Therefore, there is a problem that the cost increases.
[0004]
As another method, there is proposed a method (Japanese Patent Publication No. 42-19518) in which two components incompatible with each other are mixed and spun and then one component is eluted and removed. Since the contact surface of the compatible polymer is easy to peel off, the card passing property is insufficient, and the fineness of the obtained fiber tends to be small, and the fiber length is also random and short, so there is a problem that it cannot be used depending on the application. is there.
[0005]
In addition, a method in which two kinds of incompatible polymers are combined and spun into a sea-island or radial or layered alternately laminated structure, and then one component is eluted and removed (Japanese Patent Publication No. 47-30723, Japanese Patent Laid-Open No. 4-153321). Etc.) has also been proposed. According to this method, an ultrafine fiber having a moderate fineness and a long fiber length (filament-like) can be obtained. However, since it is necessary to elute and remove sea components, the productivity is low and the elution process is complicated and expensive. There is a problem of becoming something.
[0006]
As another method, a composite fiber obtained by alternately laminating two or more kinds of polymers in a radial or layered manner is divided by a difference in thermal expansion / shrinkage characteristics or a mechanical impact force (Japanese Patent Laid-Open No. Sho 62-133164). Has been proposed. However, in this method, not only is the partitionability inferior, but there is a problem that it is necessary to use a plurality of polymers, and the production facilities are complicated and productivity is lowered.
[0007]
Furthermore, after a suitable additive is added to the polymer to form a hollow fiber, an alkali weight loss treatment or the like is performed to separate the bonded polymers when the hollow portion is formed (Japanese Patent Laid-Open No. 8-325945). However, since this method is limited to the joint portion of the hollow nozzle hole used by the divided portion, there is a limit to making it into an ultrafine fiber by dividing into multiple portions. . Moreover, since an alkali weight reduction process is required, there also exists a problem that a use is limited.
[0008]
As described above, it is the actual situation that the ultrafine fibers that can be used in a wide range of fields cannot be efficiently produced by the conventionally proposed splitting method or the one-component elution method.
[0009]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described problems of the prior art, and its purpose is to have excellent handleability when producing a fiber product such as a card process and to easily divide it into ultrafine fibers by mechanical stress. It is to provide a multi-divided hollow polyester fiber capable of forming
[0010]
Another object of the present invention is to provide a woven or knitted fabric excellent in heat retention and texture, a soft textured artificial leather, and a nonwoven fabric such as paper texture or filling with a soft texture.
[0011]
[Means for Solving the Problems]
According to the studies by the present inventors, the object of the present invention is that the copolymer component having a sulfonate group was copolymerized in an amount of 1 to 6 mol% based on the total acid component.Intrinsic viscosity is 0.35-0.70In hollow polyester fibers made of ethylene terephthalate-based polyester, the fineness of the fibers is 0.5 to 8.0 denier, the hollowness is 25% or more, the crystallinity is 20% or more, and the crystal size of the (010) plane is 4 nm or more. And the hollow fiber was found to be achieved by a multi-divided hollow polyester fiber characterized by the presence of a plurality of discontinuous divided holes arranged in the fiber axis direction.
[0012]
Further, according to the study by the present inventors, the other object of the present invention is as follows:
(1) A woven or knitted fabric excellent in heat retention and feel, in which at least 20% by weight of the constituent fibers of the woven or knitted fabric is an ultrafine fiber obtained by dividing the multi-divided hollow polyester fiber,
(2) Artificial leather excellent in texture, in which at least 20% by weight of the constituent fibers of the artificial leather is an ultrafine fiber obtained by dividing the multi-divided hollow polyester fiber,
(3) A nonwoven fabric having a soft texture, in which at least 30% by weight of the constituent fibers of the nonwoven fabric is an ultrafine fiber formed by dividing the multi-divided hollow polyester fiber,
Was found to be achieved.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The hollow polyester fiber of the present invention is ethylene terephthalate having ethylene terephthalate as a main repeating unit and a copolymer component having a sulfonate group copolymerized in an amount of 1 to 6 mol%, preferably 2 to 5 mol% based on the total acid component. It is important to be made of a copolyester. When the amount of the copolymerization component having a sulfonate group is less than 1 mol%, it becomes difficult to form the divided holes arranged in the fiber axis direction in the hollow wall, and the hollow wall is not affected even if mechanical stress is applied. It is difficult to divide the fiber and it becomes impossible to make ultrafine fibers. On the other hand, when the amount of the copolymer component exceeds 6 mol%, although it is possible to form the divided holes arranged in the fiber axis direction in the hollow wall, it is preferable because the process stability at the time of spinning is reduced. Absent.
[0014]
The copolymer component having a sulfonate group that is preferably used includes 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-sodium sulfo-2,6. -Naphthalenedicarboxylic acid and ester-forming derivatives thereof can be mentioned, and these may be used alone or in combination of two or more.
[0015]
Such a polyester according to the present invention may be copolymerized with a copolymer component other than the above within a range not impairing the object of the present invention, and the ratio is usually 10 mol% or less based on the total acid component. is there. Examples of components that can be copolymerized include, as acid components, aromatic dicarboxylic acids such as isophthalic acid, diphenyldicarboxylic acid, and naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid, parahydroxybenzoic acid, 4 Examples include oxycarboxylic acids such as-(β-hydroxyethoxy) benzoic acid, and examples of the diol component include aliphatic diols such as 1,3-propanediol, 1,6-hexanediol, and neopentyl glycol, Examples thereof include aromatic diols such as 4-bis (β-hydroxyethoxy) benzene, and polyalkylene glycols such as polyethylene glycol and polybutylene glycol. These components may be copolymerized alone or in combination of two or more.
[0016]
If the degree of polymerization (intrinsic viscosity) of the polyester is too large, the process stability at the time of spinning tends to be low and it tends to be difficult to obtain a fine one, while if it is too small, it becomes difficult to obtain a high hollow one. Therefore, the intrinsic viscosity (IV) measured at 35 ° C. in orthochlorophenol is preferably 0.35 to 0.70, preferably 0.40 to 0.55.
[0017]
In addition, various additives may be mixed in the polyester, for example, various functionalizing agents such as antibacterial agents, hydrophilic agents, acaricides, deodorants, far-infrared radiation agents, titanium dioxide, silicon oxide, oxidation Examples thereof include inorganic fine particles such as zinc, barium sulfate, zirconium oxide, aluminum oxide, magnesium oxide, calcium oxide, and tourmaline, which may be appropriately selected and used depending on the purpose. However, when blending the inorganic fine particles, the average particle size is 1.0 μm or less, preferably 0.1 to 0.7 μm, from the viewpoint of dispersibility in the polyester. The amount is suitably in the range 1 to 10% by weight, in particular 2 to 7% by weight.
[0018]
The multi-divided hollow polyester fiber of the present invention comprising the above polyester has a single fiber fineness of 0.5 to 8.0 denier, preferably 1.0 to 4.0 denier, particularly preferably 1.5 to 3. It must be in the range of 0 denier. When the single fiber fineness is less than 0.5 denier, it is not preferable because stable production cannot be achieved and the hollow ratio of the obtained fiber tends to be small. On the other hand, if it exceeds 8.0 denier, the process stability during yarn production is good, but the thickness of the hollow wall surface in the cross section of the fiber increases, so that it becomes difficult to form the divided holes arranged in the fiber axis direction. Even if mechanical stress is applied, it is not preferable because it cannot be divided into ultrafine fibers.
[0019]
Next, the hollow ratio in the fiber cross section needs to be 25% or more, preferably in the range of 40 to 60%. If the hollowness is less than 25%, it is not preferable because it cannot be divided into ultrafine fibers even if mechanical stress is applied. On the other hand, when the hollow ratio is increased, the thickness of the hollow wall surface is decreased, hollow breakage occurs, the process stability of the yarn production is lowered, and the mechanical properties of the obtained fiber are lowered. In addition, the hollow rate here means the ratio (%) of the area of a hollow part with respect to the area enclosed by the outer peripheral part of this cross section in the fiber cross section.
[0020]
The position of the hollow portion in the fiber cross section is desirably the center of the fiber cross section, and when the eccentricity increases, it becomes difficult to uniformly divide and it is difficult to obtain a soft texture.
[0021]
Moreover, the thickness of the wall surface which comprises a hollow part is 5 micrometers or less, Especially when it exists in the range of 1.0-3.0 micrometers, the performance of the outstanding division | segmentation ultra-thinning is shown. On the other hand, if the wall surface is too thin, it becomes difficult to produce the yarn, and yarn breakage may occur in the post-processing step or the wear resistance may be lowered.
[0022]
In the multi-divided hollow polyester fiber of the present invention, in addition to the above characteristics, the crystallinity calculated from the wide-angle X-ray diffraction photograph is 20% or more, particularly in the range of 22 to 33%, and the wide-angle X In order to show good multi-splitting performance, the crystal size calculated from the half-width of the (010) plane diffraction peak of the line diffraction photograph is 4.0 nm or more, preferably in the range of 5.0 to 8.5 nm. It is essential. When the degree of crystallinity is less than 20% or the crystal size of the (010) plane is less than 4.0 nm, it is not preferable because the splitting property is lowered and it becomes difficult to make ultrafine fibers.
[0023]
The multi-divided hollow polyester fiber of the present invention needs to have a plurality of discontinuous divided holes arranged in the fiber axis direction on the hollow wall. Here, the discontinuous divided holes are holes having a finite length in the fiber axis direction and penetrating or not penetrating from the fiber surface to the hollow portion (slit shape, crack shape, etc.). In the case where such divided holes do not exist, it is not preferable because the division ultra-thinning due to mechanical stress does not proceed.
[0024]
The above-described multi-divided hollow polyester fiber according to the present invention has good mechanical properties in the fiber axis direction but is inferior in properties in the direction perpendicular to the fiber axis. In addition, 90% or more of the fibers can be divided into 4 or more, preferably 5 to 20, to make ultrafine fibers. It is preferable to perform a tension heat treatment at a temperature of 100 ° C. or higher prior to the splitting process because splitting is facilitated.
[0025]
The multi-divided hollow polyester fiber of the present invention may be a short fiber or a long fiber, and may be set as appropriate according to the purpose of use and application.
[0026]
The multi-partition hollow polyester fiber of the present invention described above can be produced, for example, by a special melt spinning method as described below. That is, the molten polyester is discharged from a spinneret having a spinning hole for producing a hollow fiber composed of a plurality of slit holes, and a temperature of 150 to 230 ° C., preferably 180, between 0 and 50 mm immediately below the spinneret. Blow heated gas at ~ 210 ° C. The spray angle is directed to the base surface at an angle of 30 to 45 degrees from the direction perpendicular to the discharge yarn traveling direction (therefore, spraying is performed in the direction opposite to the yarn traveling direction). The spraying speed is 1.0 to 5.0 m / sec, preferably 2.0 to 3.0 m / sec.
[0027]
The yarn that has passed through the heating zone is cooled and solidified after passing through a buffer zone having a length of 50 to 150 mm. For cooling and solidification, the cooling air temperature is set to 15 to 35 ° C., preferably 20 to 25 ° C., and the cooling air speed is set to 0.2 to 4.0 m / second, preferably 1.5 to 3.5 m / second. To do. The cooling range of the yarn is 100 to 450 mm, preferably 150 to 350 mm, and if it is outside this range, the quality of the resulting fiber is lowered, which is not preferable.
[0028]
Next, the cooled and solidified yarn is drawn at a spinning draft of 150 or more, preferably 150 to 500, particularly preferably 200 to 400, and a take-up speed of 500 to 2000 m / min, preferably 1000 to 1800 m / min. When the spinning draft is less than 150, the spinning stability is lowered, and at the same time, the crystal size of the (010) plane in the fiber microstructure is also not preferable. Further, when the take-up speed exceeds 2000 m / min, the crystal size of the (010) plane in the fiber microstructure increases, but it is impossible to obtain a crystal having a hollow ratio of 25% or more and satisfying the crystal size and crystallinity at the same time. On the other hand, if it is less than 500 m / min, the crystal size of the (010) plane becomes small, which is not preferable. If the spinning draft becomes too large, the stretchability in the subsequent stretching tends to be lowered, so it is desirable to make it 500 or less as described above.
[0029]
The undrawn yarn taken up in this way is drawn according to the final use, and then appropriately heat-treated. For example, in a warm water at a temperature of 50 to 70 ° C., it is stretched at a draw ratio of 2.0 to 5.0 times, and when this is not heat-set, a highly shrinkable hollow fiber is obtained, and a heating roller or a hot plate A low-shrinkage type hollow fiber can be obtained by tension heat treatment, etc., and a self-extension type hollow fiber can be obtained by performing a drawing treatment once and then heat-treating while overfeeding in warm water or the like. At the time of drawing, since the fiber has a unique fiber microstructure as described above, a large number of cracks arranged in the fiber axis direction, part of which penetrate from the fiber surface to the hollow interior, are formed discontinuously.
[0030]
As mentioned above, although an example of the manufacturing method of the multi-splitting hollow polyester fiber of the present invention has been described, the multi-splitting hollow polyester fiber of the present invention is not limited to those manufactured by the above-described method. It may be manufactured by another different method.
[0031]
The hollow polyester fiber thus obtained has good mechanical properties in the fiber axis direction, but is inferior in properties in the direction perpendicular to the fiber axis. For this reason, by applying mechanical stress, cracks are easily generated in the fiber axis direction, and 40% or more of the fibers can be divided into ultrafine fibers. At this time, for example, if heat treatment is performed in advance, the splitting property is further improved, and 90% or more of the fibers can be easily divided into four or more ultrafine fibers.
[0032]
The multi-splitting hollow polyester fiber of the present invention described above is used at 100% or mixed with other fibers (synthetic fibers such as polyester fibers other than the present invention, natural fibers such as cotton and wool). Thus, it is possible to obtain a fiber product having various excellent characteristics based on the formation of divided ultrafine fibers.
[0033]
For example, by making the multi-divided hollow polyester fiber of the present invention occupy 20% by weight or more, preferably 30% by weight or more of the woven or knitted fabric-constituting fiber, Divided ultrafine fibers occur, and a woven or knitted fabric having excellent heat retention and a soft texture can be obtained.
[0034]
Further, the multi-divided hollow polyester fiber of the present invention occupies 20% by weight or more, preferably 30% by weight or more of the artificial leather constituting fiber, whereby the multi-divided hollow fiber is divided in the artificial leather production process. An ultra-fine fiber is produced, and an artificial leather that exhibits a soft touch and is light in weight can be obtained.
[0035]
In the case of making a nonwoven fabric, the fibers of the present invention occupy 30% by weight or more, preferably 40% by weight or more, particularly preferably 50% by weight or more of the nonwoven fabric constituting fibers, so that heat retention can be achieved even if the basis weight is reduced. A non-woven fabric having an excellent and soft texture can be obtained. In the case of a wet nonwoven fabric by a papermaking method, a short-cut fiber with a fiber length of 3 to 30 mm is used, and this is beaten using a conventionally known beating machine (for example, a disc refiner), so that a fibrid shape that has been divided into multiple pieces in advance. Get fiber. At this time, the operating condition of the beating machine may be selected in accordance with the machine to be used. Next, after adding a papermaking binder to the slurry in which the fibrid fibers obtained from the multi-divided polyester hollow fibers are dispersed in water, a normal papermaking machine (long mesh papermaking machine, short meshing paper machine, circle By using a paper-type paper machine and the like, and then heating and drying with a Yankee dryer, a non-conventional uniform and soft wet nonwoven fabric can be obtained. In the case where foaming or dispersion is insufficient in the papermaking process, there is no problem even if a papermaking aid such as a commonly used dispersing agent or adhesive is used.
[0036]
The papermaking binder used here is a water-soluble adhesive substance usually used in papermaking. For example, natural water-soluble polymers such as gelatin and sodium alginate, phosphorylated starch, cyanoethylated starch, carboxymethylcellulose, hydroxypropyl Examples include semi-synthetic water-soluble polymers such as methyl cellulose, synthetic water-soluble polymers such as polyvinyl alcohol, sodium polyacrylate, polyacrylamide, and polyethylene oxide, polyphosphate, etc., which can be used alone or in combination. Can be used. It is also possible to use a synthetic latex made of a single or copolymer such as vinyl chloride, vinyl acetate, styrene, acrylonitrile, acrylate ester, butadiene, or ethylene, with a plasticizer or various stabilizers added. it can.
[0037]
The papermaking binder may be in the form of a fiber. For example, fibers that exhibit binder performance under wet heat conditions after papermaking, such as polyvinyl alcohol fibers and polyethylene oxide fibers, can be used. Furthermore, single fibers of components that are fused by a heat treatment at 80 to 170 ° C. usually performed after papermaking and exhibit an adhesive effect, such as polypropylene, chlorosulfonated polyethylene, and ethylene vinyl acetate copolymer, or these polymers Further, a heat-adhesive conjugate fiber combined with a side-by-side type or a seascore type with another polymer having a melting point higher than that of these polymers by 20 ° C. or more can also be used.
[0038]
It is necessary to use the above-mentioned fibrid fiber in an amount of 30% by weight based on the total weight of the wet nonwoven fabric from the viewpoint of the feel (flexibility) of the resulting wet nonwoven fabric. On the other hand, the papermaking binder as described above is suitably in the range of 5 to 30% by weight based on the total weight. When the amount of the binder is less than the above range, the strength as a wet nonwoven fabric is insufficient and handling becomes difficult. On the other hand, when the above range is exceeded, the fixing points between the fibers are increased, and the soft texture due to the fibrous fibers tends to be insufficient. In addition to the fibrid fiber and the binder, for example, natural pulp, synthetic pulp, polyethylene terephthalate fiber, and the like can be used in combination. If the third component is mixed in this manner, a more characteristic wet nonwoven fabric can be obtained.
[0039]
The multi-divided hollow polyester fiber of the present invention may be used at 100% or mixed with other fibers (synthetic fibers such as polyester fibers other than the present invention, natural fibers such as cotton and wool). The split ultrafine fibers can be produced without any problems, so that the above characteristics are exhibited, but various other excellent characteristics are also exhibited. For example, when the ultra fine fiber is put on a card, the card passing property is remarkably lowered. However, in the case of the multi-divided hollow polyester fiber of the present invention, first, only discontinuous division occurs in the fiber axis direction, so that it is divided. The individual ultrafine fibers are initially aggregated and do not fall apart, and behave as an ultrafine fiber aggregate. For this reason, card passability improves.
[0040]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these at all. In addition, the measurement of each characteristic value in an Example followed the following method.
[0041]
<Intrinsic viscosity>
Measurement was performed at 35 ° C. using orthochlorophenol as a solvent.
<Fineness>
It measured by JIS-L1015 7-5-1A method.
<Hollow rate>
Using the image analysis system, Pierce 2 (Pierce Co., Ltd.), the section cross-sectional image of the single fiber is magnified 500 times, and the cross-sectional area (including the hollow portion) and the hollow area of the single fiber are measured and the area is measured. It was calculated from the ratio.
[0042]
<Divided hole>
The presence or absence of a plurality of discontinuous divided holes arranged in the fiber axis direction was determined from the enlarged side view of the fiber.
<Hollow wall thickness>
The cross-sectional area of the single fiber (including the hollow part) and the area of the hollow part were measured from the above 500-fold cross-sectional image, and the thickness of the hollow wall surface was obtained by calculation, and indicated by an average value of n = 20.
<Fiber split ratio>
A cross-sectional photograph of the product was taken, 50 single yarns were randomly selected from the photograph, and the ratio at which the hollow wall was divided at four or more locations was determined.
<Average number of hollow divisions of hollow fiber>
Ten single yarns were randomly selected from the above cross-sectional photograph, and the number of each hollow fiber divided was measured to obtain an average value.
[0043]
<Crystallinity>
It calculated | required according to the usual method from the wide-angle X-ray-diffraction image.
<(010) plane crystal size>
It calculated | required in accordance with the usual method from the (010) plane diffraction peak half width of the wide-angle X-ray-diffraction image.
[0044]
<Spinnability and stretchability>
Spinnability was evaluated according to the following criteria.
Good (O): Number of yarn breakage <0.1 times / weight / day, Adhesive yarn <0.1 / weight / day
Slightly poor (△): Number of yarn breakage is 0.1 to 0.2 times / weight / day and adhesion yarn is 0.1 to 0.2 weight / day / day
Defective (×): Number of yarn breaks> 0.2 times / weight / day, close contact yarn> 0.2 pieces / weight / day
However, the term “adhesive yarn” as used herein means a yarn in which two or more single yarns are fused.
[0045]
The stretchability was evaluated according to the following criteria.
Good (O): Rolled by single yarn breakage <1 time / unit / day, number of undrawn yarns generated <5 / 100,000
Slightly defective (△): Rolling of roller due to breakage of single yarn is 1 to 3 times / unit / day, number of undrawn yarns is 5 to 10 thousand / 100,000
Defective (×): Rolled by roller due to breakage of single yarn> 3 times / unit / day, number of undrawn> 10 / 100,000
[0046]
<Heat retention>
The thermal conductivity is measured according to JIS A 1412, and the product having a low thermal conductivity and excellent heat retention (thermal conductivity is 0.048 kcal / m · h · deg or less) is ranked A, and the good one (thermal conductivity A rate of 0.048 to 0.055 kcal / m · h · deg) is rank B, and a normal product (thermal conductivity 0.055 to 0.060 kcal / m · h · deg) is rank C, inferior (Thermal conductivity is more than 0.060 kcal / m · h · deg) as D rank, and determined by ranking.
[0047]
<Lightweight fabric>
Same fabric weight (5cm area)2) Was measured, the volume was calculated by measuring the thickness of the base fabric, and the lightness was determined by relative comparison using a standard hollow fiber with a fineness of 1.5 de and a hollowness of 30% as a standard. An article with excellent lightness was ranked as A rank, a good article as B rank, an ordinary article as C rank, and an inferior article as D rank.
[0048]
<Soft touch feeling such as woven and knitted fabrics, non-woven fabrics, cool feeling, drape, and feeling of bottom>
Sensory evaluation was performed based on the feeling of touch, and an excellent product was ranked as A, a good product as B rank, a normal product as C rank, and an inferior product as D rank.
[0049]
<Initial bulk of nonwoven fabric>
The JIS-L1097 specific volume (initial bulkiness) method was followed.
First, the raw cotton is hung on a card to prepare a web having a size of a test piece of 20 cm × 20 cm and a mass (w) of about 40 g, which is left for 1 hour. Next, 0.5 g / cm is applied to the test piece.2The load plate (size: 20 cm × 20 cm) is placed, and 2 kg of the weight (A) is further placed thereon and left for 30 seconds, and then the weight (A) is removed and left for 30 seconds. This operation was repeated three times, the height of the four corners of the load plate after being left for 30 seconds without the weight (A) was measured, and the average value (h0mm) and the initial volume is calculated from the following formula.
Initial bulk (cmThree/ G) = (20 × 20 × h0/ 10) / w
[0050]
<Nonwoven fabric initial pressure bulk>
It measured according to the JIS-L-1097 specific volume (crushability) method.
First, 0.5 g / cm is applied to the test piece when measuring the initial bulk of the nonwoven fabric.2The load plate (size: 20 cm × 20 cm) was placed, and 4 kg of weight (B) was placed for 30 seconds, and then the height of the four corners of the thick plate was measured and the average value (h1mm) and the specific performance (initial pressure bulkiness) is calculated from the following formula.
Initial pressure bulk (cmThree/ G) = (20 × 20 × h1/ 10) / w
[0051]
<Bending hardness>
Sample direction when a test piece of width 2.5 cm x length 9 cm is gripped at a position 2 cm from the end, bent at a position 2 cm from the other end, and the test piece is gripped and fixed for the first time The repulsive force when it is bent 90 ° from is measured with a strain gauge (digital hose gauge), and the repulsive force is converted into a value of 1 cm width of the test piece.
[0052]
<Card passability>
2 kg of raw cotton was passed through a flat card at a card speed of 50 m / min and evaluated according to the following criteria.
◎: Card clogging, web breakage, nep does not occur, and card passing is good
○: Card clogging and web breakage are not observed, but slight neps are observed.
Δ: Card is not clogged, but some web breaks and neps are observed
×: Card jam, web break, nep, etc. are observed
[0053]
<Spinning>
The following criteria were evaluated according to the passing state of the spinning process (card, eyelash, roving, fine spinning).
◎: Passes through the entire process without any problems
○: Passes through card, eyelash and roving process without any problems
△: Passes through the card and eyelash process
×: Only the card process passes
[0054]
<Bending rigidity (kg / cm2)>
60 x bending hardness (g / cm) / [test specimen thickness (mm)]Three
<Buckling>
A test piece of 20 cm × 20 cm is bent to a radius of curvature of about 5 mm, and the bent portion is gradually moved while grasping the bent portion with a fingertip, and the rounded state of the bent portion is observed.
Class with roundness and no corners is considered good, and corners are considered bad. The next four stages are: excellent, ◎, good, ○, normal, △, inferior, and x. And evaluated.
[0055]
<Leather-like properties>
Measure a repulsive force with a strain gauge when the test piece of width 2.5cm x length 9cm is folded in half, and folded and compressed to 3 times the thickness of the test piece. The value per 1cm width (g / cm) expressed. The larger this value, the better the leather-like property.
[0056]
<Bending durability>
It was measured according to JIS-K-6505-525.
[0057]
<Cut length>
It measured according to JIS-P-8113 (the tensile strength test method of paper and paperboard).
[0058]
<Tearing>
The tear strength was measured according to JIS-L-1096 (General Textile Testing Method).
[0059]
[Example 1]
A polyethylene terephthalate copolymer polyester having a titanium oxide content of 0.07% by weight, an intrinsic viscosity of 0.45, and a copolymerization amount of 5-sodium sulfoisophthalic acid component (SIP) of 4.5 mol% is hollow. Extruded from a spinneret having a mold nozzle of 2000 holes at a polymer temperature of 268 ° C. and a discharge rate of 1600 g / min, taken at a spinning speed of 1800 m / min, and a single fiber fineness of 4.0 denier and a hollow rate of 50% Got.
[0060]
At this time, hot air having a temperature of 200 ° C. and a wind speed of 3.5 m / second is blown at a blowing angle of 35 degrees directly from 0 to 50 mm immediately below the hollow nozzle (eight slit holes), and passes through a buffer zone having a length of 100 mm. Then, cooling air having a temperature of 25 ° C. and a wind speed of 3.5 m / sec was blown over a length of 250 mm.
[0061]
The hollow undrawn yarn obtained was stretched in one step with warm water at a temperature of 65 ° C. and a draw ratio of 2.80 times, subjected to tension heat treatment with a heating roller at 140 ° C., and subsequently subjected to mechanical crimping of 12 pieces / 25 mm. Then, after heat setting with hot air of 120 ° C., it was cut into a predetermined length to obtain short fibers. The obtained hollow polyester short fibers had a fineness of 1.5 denier and a hollowness of 50%, and a plurality of discontinuous divided holes arranged in the fiber axis direction were present on the surface. The evaluation results of the obtained fiber are shown in Table 1.
[0062]
[Examples 2-3, Comparative Examples 1-5]
In Example 1, an undrawn yarn was obtained in the same manner as in Example 1 except that the amount of SIP copolymerization and intrinsic viscosity were changed as shown in Table 1, and the heating and cooling conditions were changed as shown in Table 1.
The undrawn yarn was drawn and heat-treated under the conditions shown in Table 1, and was subjected to crimping and then cut in the same manner as in Example 1 to obtain short fibers. These evaluation results are shown in Table 1.
[0063]
[Table 1]
[Examples 4-7, Comparative Examples 6-7]
A hollow polyester short fiber (fiber length: 38 to 100 mm) having the characteristics shown in Table 2 was spun into an English cotton 30 with a twist number of 17.1 times / 25 mm by a ring spinning method. The spun yarn was woven into a plain woven fabric having a weaving density (87 warp / 25 mm, 68 weft / 25 mm) and a width of 127 mm, scoured by a conventional method, and dyed with a disperse dye. In addition, Example 7 mixes with cotton (cotton). The obtained fabric characteristics are shown together in Table 2.
[0065]
[Table 2]
[Examples 8 to 10, Comparative Examples 8 to 9]
High shrinkage type and self-extension type hollow polyester short fibers (fiber length 38 to 64 mm) having the characteristics shown in Table 3 are mixed in the proportions shown in Table 3 to form a web, and then No. 40 regular barb is 1 800 / cm in a needle locker room equipped with needles2Punching with a driving density of 157 g / cm2A non-woven fabric was obtained. This non-woven fabric was immersed in warm water at 68 ° C. for 2 minutes to shrink the nonwoven fabric by 35% in terms of area shrinkage. Next, after vacuum dehydration, it was dried at 50 ° C. for 5 minutes, and the basis weight was 242 g / cm.2A non-woven fabric was obtained. This non-woven fabric was held at 180 ° C. for 60 seconds between a heated metal drum and a 60-mesh stainless steel net belt, with a thickness of 1.2 mm and an apparent density of 0.202 g / cm.ThreeA non-woven fabric, and then a non-woven fabric obtained by adding 5 parts of carbon black to 100 parts of polyurethane resin in a 12% dimethylformamide solution of polyurethane resin (Chrisbon MP-185: manufactured by Dainippon Ink Chemical Co., Ltd.) Then, after squeezing with a squeeze roll, it was immersed in warm water at 40 ° C. to be solidified, further washed until almost no solvent was present, and dried to obtain an artificial leather. The results are shown in Table 3.
[0067]
[Table 3]
[Examples 11-15, Comparative Examples 10-11]
A hollow polyester short fiber (fiber length: 51 mm) having the characteristics shown in Table 4 is put on a card to form a web, and the basis weight is 60 g / m.2The nonwoven fabric was made. The results are shown in Table 4.
[0069]
[Table 4]
[Examples 16 to 19, Comparative Examples 12 to 13]
Multi-divided hollow polyester fiber not imparted with crimp in Example 1 (fineness 1.5 de, fiber length 5 mm, hollow rate 50%, crystallinity 30%, crystal size 8.5 nm, discontinuous divided pores) ) Was divided into multiple portions by a disc refiner (bath ratio 1: 100 (weight ratio of fiber to water)). A side-by-side type composite composed of terephthalic acid / isophthalic acid / ethylene glycol / diethylene glycol copolymer polyester and polybutylene terephthalate having a heat fusion temperature of about 120 ° C. as a binder in the water slurry of the multi-segmented fibers. A normal polyester fiber (fineness 0.5 de, fiber length 5 mm, zero crimp) is represented as a fiber (fineness 1.5 de, fiber length 5 mm, crimped number zero) and the third component (main fiber as well as fibrid fiber). 5 is mixed and the basis weight is about 50 g / m.2The paper was hand-made so that a wet nonwoven fabric was obtained by drying and heat-sealing with a Yankee dryer. The results are shown in Table 5.
[0071]
[Table 5]
【The invention's effect】
Since the multi-divided hollow polyester fiber of the present invention described in detail above can easily be cracked in the fiber axis direction due to mechanical stress to be divided into ultrafine fibers, for example, when used for woven or knitted fabric, heat retention And a knitted or knitted fabric having a soft texture is obtained. In addition, when used as a base fabric for artificial leather, in addition to a soft texture by making ultrafine fibers, an artificial leather product rich in light weight can be obtained. Furthermore, when used for nonwoven fabrics, a nonwoven fabric with a soft texture in addition to the light-weight heat retaining effect by dividing ultrafine fibers can be obtained. Especially in the case of paper-made paper (wet nonwoven fabric), the texture (surface) ) Is also good.
[Brief description of the drawings]
FIG. 1 shows an example of a cross section of a multi-divided hollow polyester fiber of the present invention.
FIG. 2 shows an example of a side surface of the multi-divided hollow polyester fiber of the present invention.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09619199A JP4130035B2 (en) | 1998-04-30 | 1999-04-02 | Multi-divided hollow polyester fiber and woven / knitted fabric, artificial leather and nonwoven fabric using the fiber |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12052098 | 1998-04-30 | ||
| JP10-120520 | 1998-04-30 | ||
| JP09619199A JP4130035B2 (en) | 1998-04-30 | 1999-04-02 | Multi-divided hollow polyester fiber and woven / knitted fabric, artificial leather and nonwoven fabric using the fiber |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000017519A JP2000017519A (en) | 2000-01-18 |
| JP2000017519A5 JP2000017519A5 (en) | 2005-12-22 |
| JP4130035B2 true JP4130035B2 (en) | 2008-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09619199A Expired - Fee Related JP4130035B2 (en) | 1998-04-30 | 1999-04-02 | Multi-divided hollow polyester fiber and woven / knitted fabric, artificial leather and nonwoven fabric using the fiber |
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| Country | Link |
|---|---|
| JP (1) | JP4130035B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4495874B2 (en) * | 2001-03-13 | 2010-07-07 | 帝人ファイバー株式会社 | Split hollow polyester fiber |
| JP4563626B2 (en) * | 2001-09-07 | 2010-10-13 | 帝人ファイバー株式会社 | Splittable polyester fiber |
| KR100479988B1 (en) * | 2002-07-24 | 2005-03-30 | 미래산업 주식회사 | Method for compensating temperature in semiconductor test handler |
| DE10258112B4 (en) * | 2002-12-11 | 2007-03-22 | Carl Freudenberg Kg | Process for producing a sheet from at least partially split yarns, fibers or filaments |
| JP4907953B2 (en) * | 2005-11-02 | 2012-04-04 | 帝人ファイバー株式会社 | Filling and textile products |
| JP5057822B2 (en) * | 2007-03-29 | 2012-10-24 | 株式会社クラレ | Method for producing long-fiber nonwoven fabric and method for producing base material for artificial leather |
| JP5586452B2 (en) * | 2010-12-28 | 2014-09-10 | 富士フイルム株式会社 | Method for producing void-containing yarn |
| CN112760825A (en) * | 2020-12-31 | 2021-05-07 | 常州锦欣达纤维新材料有限公司 | Single-layer melt-blown fabric production system with low resistance and high filtering effect and production method |
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1999
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| JP2000017519A (en) | 2000-01-18 |
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