JP3583402B2 - Polyester fiber - Google Patents

Description

【００１４】
本発明は、ＰＥＳ（Ｉ）を一成分とした複合繊維である。
【００１５】
本発明は、ＰＥＳ繊維（ＩＩ）を一成分とした異収縮混繊糸である。
【００１６】
本発明は、ＰＥＳ繊維（Ｉ）からなるステープルを一成分とする混合紡績糸である。
【００１７】
【発明の実施の形態】
上記ＰＥＳ（Ｉ）に含有される、構造式（１）で示される化合物において、エステル形成性官能基としては、ヒドロキシ基、ヒドロキシアルキル基、カルボキシル基、そのエステル形成性誘導体が挙げられる。ヒドロキシアルキル基を構成するアルキルに限定はないが、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基等の炭素数が１〜４のアルキルが好ましく、分岐したアルキルでもよい。また、カルボキシル基のエステル形成性誘導体とは、カルボキシメチル基、カルボキシエチル基、カルボキシプロピル基、カルボキシブチル基等炭素数１〜４のアルキルが好ましい。
そして、該化合物は１つまたは２つのエステル形成性官能基を有していることが必要であり、ポリエステル分子鎖中に共重合されることがポリエステル繊維として高い収縮特性の発現、重合性等の点で好ましく、エステル形成性官能基の数は２つであることが好ましい。その場合、エステル形成性官能基は同じ種類の基であっても異なった種類の基であってもよい。
【００１８】
さらに、該化合物においてエステル形成性官能基が結合している以外の炭素には水素原子、アルキル基が結合しているが、重合性を阻害しない点でエステル形成性官能基が結合している以外の炭素には水素原子が結合していることが好ましい。なお、アルキル基としてはメチル基、エチル基、プロピル基、ブチル基、ペンチル基等の炭素数１〜５のアルキル基が挙げられ、該基は分岐していてもよい。
【００１９】
このような化合物として、ノルボルナン２，３−ジメタノール、ノルボルナン２，３−ジエタノール、ノルボルナン２，３−ジカルボン酸、ノルボルナン２，３−ジカルボン酸ジメチルエステル、ノルボルナン２，３−ジカルボン酸ジエチルエステル、パーヒドロジメタノナフタレンジメタノール、パーヒドロジメタノナフタレンジエタノール、パーヒドロジメタノナフタレンジカルボン酸、パーヒドロジメタノナフタレンジカルボン酸ジメチルエステル、トリシクロデカンジメタノール、トリシクロデカンジエタノール、トリシクロデカンジカルボン酸、トリシクロデカンジカルボン酸ジメチルエステル、トリシクロデカンジカルボン酸ジエチルエステル等が挙げられ、これらの化合物においてエステル形成性官能基が結合している以外の炭素にアルキル基が結合した化合物も挙げられる。また、アルキル基以外の化合物としてスルホニル基等の他の置換基が結合してる化合物も本発明には包含される。上述の化合物の中でも重合性、製糸性、繊維強度、収縮性能の点でノルボルナン２，３−ジメタノール、ノルボルナン２，３−ジカルボン酸、ノルボルナン２，３−ジカルボン酸ジメチルエステル、パーヒドロジメタノナフタレンジメタノール、パーヒドロジメタノナフタレンジカルボン酸、パーヒドロジメタノナフタレンジカルボン酸ジメチルエステル、トリシクロデカンジメタノール、トリシクロデカンジエタノール、トリシクロデカンジカルボン酸、トリシクロデカンジカルボン酸ジメチルエステルが好ましい。さらに重合性の観点から見ると、ノルボルナン２，３−ジメタノール、ノルボルナン２，３−ジカルボン酸、ノルボルナン２，３−ジカルボン酸ジメチルエステル、パーヒドロジメタノナフタレンジメタノール、パーヒドロジメタノナフタレンジカルボン酸、パーヒドロジメタノナフタレンジカルボン酸ジメチルエステルは２つのエステル形成性官能基がトランス位に位置することが好ましい。
【００２０】
本発明におけるポリエステルとは、テレフタル酸を主たるジカルボン酸成分とし、エチレングリコ−ル、トリメチレングルコール、テトラメチレングリコールから選択された少なくとも１種のアルキレングリコールを主たるグリコール成分とするポリエステルである。また本発明の目的を損なわない範囲内で構造式（１）で示される化合物以外に第３成分を共重合させても差支えない。
かかる第３成分として、イソフタル酸、フタル酸、ナフタレンジカルボン酸、ビフェニルジカルボン酸、４，４′−ジフェニルエ−テルジカルボン酸、４，４′−ジフェニルメタンジカルボン酸、４，４′−ジフェニルスルホンジカルボン酸、４，４′−ジフェニルイソプロピリデンジカルボン酸、１，２−ジフェノキシエタン−４′，４″−ジカルボン酸、アントラセンジカルボン酸、２，５−ピリジンジカルボン酸、ジフェノキシケトンジカルボン酸、５−ナトリウムスルホイソフタル酸、ジメチル−５−ナトリウムスルホイソフタレート、５−テトラブチルホスホニウムスルホイソフタル酸等の芳香族ジカルボン酸；マロン酸、コハク酸、アジピン酸、アゼライン酸、セバシン酸等の脂肪族ジカルボン酸；デカリンジカルボン酸、シクロヘキサンジカルボン酸等の脂環族ジカルボン酸；β−ヒドロキシエトキシ安息香酸、ｐ−オキシ安息香酸、ヒドロキシプロピオン酸、ヒドロキシアクリル酸等のヒドロキシカルボン酸；これらのエステル形成性誘導体から誘導されたカルボン酸、ε−カプロラクトン等の脂肪族ラクトン；ヘキサメチレングリコ−ル、ネオペンチルグリコ−ル、ジエチレングリコ−ル、ポリエチレングリコ−ル等の脂肪族ジオ−ル；ヒドロキノンカテコ−ル、ナフタレンジオ−ル、レゾルシン、ビスフェノ−ルＡ、ビスフェノ−ルＡのエチレンオキサイド付加物、ビスフェノ−ルＳ、ビスフェノ−ルＳのエチレンオキサイド付加物等の芳香族ジオ−ル；シクロヘキサンジメタノ−ル等の脂肪族ジオ−ルなどを挙げることができる。これらの第３成分は１種のみまたは２種類以上が共重合されていてもよい。
【００２１】
本発明のＰＥＳ（Ｉ）には、ポリエステルが実質的に線状である範囲内でトリメリット酸、トリメシン酸、ピロメリット酸、トリカルバリル酸等の多価カルボン酸；グリセリン、トリメチロ−ルエタン、トリメチロ−ルプロパン、ペンタエリスルト−ル等の多価アルコ−ルが共重合されていてもよい。
【００２２】
構造式（１）で示される化合物の含有量はポリエステルを構成するジカルボン酸成分に対して２〜２０モル％、好ましくは３〜１８モル％の範囲である。該含有量が２モル％未満の場合、ポリエステルの結晶化度の低下、繊維の収縮率の上昇が不十分であることから、所期の目的の繊維が得られない。一方、含有量が２０モル％を越える場合、ポリエステルの重合性が低下するとともに、結晶性のポリエステルが得られにくくなり、たとえ得られたとしてもポリエステルの融点が低くなり、ポリエステル繊維に要求される耐熱性を満足するものではない。
また該化合物の含有量が増す程、ポリエステルの結晶化度および融点が低下するが、該ポリエステル繊維の収縮率は上昇する傾向にあるので、繊維各用途に要求される耐熱性、収縮性能、染色性等を考慮して本発明の範囲内で含有量を変化させればよい。
本発明に係わるポリエステルは、通常の方法で重合することができる。たとえば、テレフタル酸とアルキレングリコールを直接エステル化させるか、テレフタル酸ジメチル等のテレフタル酸の低級アルキルエステルとアルキレングリコ−ルとをエステル交換反応させるか、またはテレフタル酸とアルキレンオキシドとを反応させるかしてテレフタル酸のアルキレングリコ−ルエステルおよび／またはその低重合体を生成させる第一段階の反応、そして第一段階で得られた反応生成物を、三酸化アンチモン、酸化ゲルマニウム、テトラアルコキシエタン等の重合触媒を用いて、減圧下２３０〜３００℃で所望の重合度になるまで重縮合反応させる第二段階の反応によって製造される。その際、構造式（１）で示される化合物の所望量を重縮合反応が終了するまでの任意の段階、たとえばポリエステルの出発原料に添加したり、エステル交換反応後で重縮合反応前に添加することができる。
また、ポリエステルの重合度を高めるために液相で重合を行なった後に固相重合を行うことも可能である。
【００２３】
本発明のＰＥＳ（Ｉ）は固有粘度〔フェノ−ル／テトラクロロエタン（重量比５０／５０）の混合溶媒を用い、３０℃で測定〕が０．４〜１．５の範囲であることが好ましい。該ＰＥＳ（Ｉ）の固有粘度が０．４未満の場合、繊維化した場合の繊維強度、収縮特性が不十分となり、所期の目的が奏されにくい。一方、該ＰＥＳ（Ｉ）の固有粘度が１．５を越えるとポリエステルの溶融粘度が高くなり過ぎ、紡糸・延伸等の製糸性が悪化していくので好ましくない。
【００２４】
本発明のＰＥＳ（Ｉ）には、必要に応じ、本発明を損なわない範囲内で酸化防止剤、紫外線吸収剤、蛍光増白剤、艶消剤、帯電防止剤、難燃剤、難燃補助剤、潤滑剤、着色剤、可塑剤、無機充填剤等の添加剤が配合されていてもよい。
【００２５】
ＰＥＳ繊維（ＩＩ）は、一般的な溶融紡糸法によって容易に繊維化することができる。得られた紡糸原糸は通常の方法で延伸すればよく、通常のポリエステル繊維の延伸条件で延伸することができる。延伸は加熱ロ−ラ−で予熱後、巻取ロ−ラの速度に応じる延伸倍率で延伸して熱処理することによりなされる。またスピンドロ−のような紡糸延伸が直結した方法で延伸して熱処理してもよい。
【００２６】
該ＰＥＳ繊維（ＩＩ）の横断面は、円形、三葉形〜八葉形などの多葉形、Ｔ字形、Ｖ字形、扁平形、方形等の異形の任意の断面形状であることができ、また中実繊維に限らず、中空繊維や多孔質繊維であってもよい。繊維の太さ（繊度）もとくに限定されず、所期の目的に応じて任意の太さ（繊度）にすることができる。また、ＰＥＳ繊維（ＩＩ）は繊維軸方向に繊度斑を有していてもよい。
また、ＰＥＳ繊維（ＩＩ）はフィラメントのみならず、ステープルファイバーとしても利用できる。
【００２７】
このようにして得られたＰＥＳ繊維（Ｉ）は複屈折率Δｎが下記式（２）を満足するものである。
−５．５５×Ａ＋８０≦Δｎ×１０^３≦−５．５５×Ａ＋１６５ （２）
〔ただし、Ａは構造式（１）で示される化合物の含有量（モル％）である。〕
複屈折率Δｎがかかる範囲内にあることにより、該ポリエステル繊維は染色した場合の染色性、深色性に優れているのである。
【００２８】
また、構造式（１）で示される化合物をポリエステルの分子鎖に含有させることにより、該分子鎖に対し、該化合物の脂肪族環状骨格が側鎖として位置するような構造をとることから、該化合物の含有量が低くても非晶性が増し、二次転移点温度の低下が抑制され、熱を受けて繊維が収縮する際、繊維内部の緩和時の応力が蓄積されるため高収縮であり、しかも耐熱性、染色堅牢度、耐光性に優れた繊維となるのである。かかる耐光性は、カーボンアーク灯に対する耐光堅牢度として示すことができ、上記のＰＥＳ繊維（ＩＩ）は４級以上である。またこの際の染色条件はとくに限定されるものではなく、あらゆる分散染料、カチオン染料、酸性染料によって薄色から濃色にわたって染色された繊維に対して有効である。
【００２９】
ＰＥＳ繊維（ＩＩ）は延伸条件によって高収縮率のみならず、高収縮応力をも有することができる。
一般的に高い収縮率を有する繊維の収縮応力は低いものであるが、本発明のポリエステル繊維は延伸条件によって高収縮率および高収縮応力を合わせ持つものである。
すなわち、一般的な溶融紡糸法によって紡糸されたポリエステル繊維はいったん捲取られた後、または捲取ることなく延伸に供され、延伸は熱延伸にて行われる。延伸ゾーンに供給される前に７５〜９５℃程度の温度の加熱ローラで予熱することが好ましい。そして１５０℃以下の温度、好ましくは１４０℃以下の温度で切断延伸倍率の０．６８倍以上、好ましくは０．７０倍以上の延伸倍率で延伸される。延伸温度が１５０℃を越えると収縮率が低下し、延伸倍率が切断延伸倍率の０．６８倍未満の場合、十分な熱収縮応力を有する繊維が得られないばかりか、残留伸度が大きすぎ衣料用繊維としては使用できにくい。
【００３０】
このようにして延伸して得られた延伸ポリエステル繊維〔以下、延伸ＰＥＳ繊維（ＩＩＩ）と称する〕は、１８０℃における乾熱収縮率が２０％以上、乾熱最大収縮応力が２５０ｍｇ／ｄ以上、かつ９８℃における湿熱収縮率が１５％以上という、高い収縮率、高い収縮応力を有するのである。乾熱収縮率、乾熱最大収縮応力、湿熱収縮率の３者を同時に満足することにより、後述する芯鞘加工糸の芯部フィラメントとして、また異収縮混繊糸の一成分として用いると、風合いが良好で、後加工により適度な張り腰と反発感、膨らみを有する織編物等の布帛を得ることができるのである。
１８０℃における乾熱収縮率が２０％未満の場合、該延伸ＰＥＳ繊維（ＩＩ）を後述の芯鞘加工糸の芯部フィラメントとして利用し、織編物に形成したものは十分な収縮が発現せず、嵩高性が不満足なものとなりやすい。乾熱収縮率の上限についてはとくに限定はないが、糸質の劣化を考慮すると、８０％以下であることが好ましい。とくに２０〜７５％の範囲であることがより好ましい。
また９８℃における湿熱収縮率が１５％未満の場合、上述の乾熱収縮率との差が大きくなり、このような延伸ＰＥＳ繊維（ＩＩ）を用いたを織編物は、その加工時、たとえば熱水処理、染色等の湿熱処理後の熱セット等の乾熱処理での収縮が大きすぎるために形態安定性、形態均質性に欠けたものとなってしまいやすい。湿熱収縮率の上限については特に限定はないが、繊維物性、とくに織編物等の布帛のへたり等を考慮すると、７５％以下であることが好ましい。とくに１５〜７０％の範囲であることがより好ましい。そして、乾熱収縮率と湿熱収縮率の差についてはとくに限定されないが、上述の理由により、１〜３０％の範囲であることが好ましい。
さらに、収縮応力は、拘束下にある糸や織編物の収縮の起こり易さを左右するため、収縮応力が大きい程拘束下でも収縮しやすい。１８０℃における乾熱最大収縮応力が２５０ｍｇ／ｄ以上であると拘束下でも十分収縮するのである。
【００３１】
該延伸ＰＥＳ繊維（ＩＩＩ）の利用方法として、異収縮混繊糸、芯鞘加工糸がある。
まず、異収縮混繊糸への利用について説明する。
従来、収縮率の異なるポリエチレンテレフタレート繊維からなる異収縮混繊糸はソフト感とドレープ性に富んだシルクライクな織編物用として、婦人用ドレス、ブラウス等を中心に使用されている。このような混繊糸は、沸水収縮率の異なる延伸糸の混繊、同一物性の未延伸糸を熱処理条件を変えて延伸し混繊することによって得られている。しかしながら、これらの方法では単に沸水収縮率差を設けて混繊糸としているに過ぎず、製織編までの熱履歴により熱収縮率差が初期よりも小さくなり、さらには織編物とした場合、その織編拘束の中で熱収縮率差に起因して蓄積される応力が小さいので、風合の乏しいものとなる。
このような従来の異収縮混繊糸において、上記の延伸ＰＥＳ繊維（ＩＩＩ）を高収縮繊維として用いると、上記の問題点が解決されるうえに耐光性という実用性能が大きく優れるのである。
異収縮混繊糸は、上記の延伸ＰＥＳ繊維（ＩＩＩ）を高収縮繊維群に、かかる延伸ＰＥＳ繊維（ＩＩＩ）よりも収縮率の低い繊維を低収縮繊維群として、これらの繊維群が混繊交絡または混合紡糸されてなる。高収縮繊維群と低収縮繊維群との９８℃における湿熱収縮率（以下、単に湿熱収縮率と称する）差は８％以上であることが好ましい。該湿熱収縮率差が８％未満の場合、織編物とした後の工程で十分な熱収縮挙動が得られにくい。すなわち、織編物にした後で芯部に高収縮繊維群を配置させ、鞘部に低収縮繊維群を配置させた特定の構造を形成させるためには、高収縮繊維群と低収縮繊維群との湿熱収縮率差のみを目安とするだけでは不十分であり、高収縮繊維群と低収縮繊維群の湿熱収縮率差と高収縮繊維群の最大乾熱収縮応力との相乗効果により、織編物にした後の工程で十分な熱収縮挙動を起こし、張り、腰、膨らみ感等の風合いが良好となるのである。
織編物にした後の工程で十分な熱収縮挙動を起こすためには、高収縮繊維群と低収縮繊維群の湿熱収縮率差が８〜６０％、とくに１０〜５５％の範囲にあることが好ましい。
【００３２】
また、かかる異収縮混繊糸は、湿熱収縮率が１０〜５５％、とくに１０〜５０％の範囲であることが好ましい。該湿熱収縮率が１０％未満の場合、織編物にした時の張り、腰、膨らみ感等の風合が不十分であり、一方５５％を越えると混繊糸の熱安定性が劣る場合がある。
【００３３】
さらに、該混繊糸を構成する高収縮繊維群の各繊維、すなわち延伸ＰＥＳ繊維（ＩＩＩ）の単糸繊度は１〜１０デニール、低収縮繊維群の単糸繊度は５デニール以下が好ましく、高収縮繊維群と低収縮繊維群との重量比は前者：後者＝２：１〜１：５の範囲であることが織編物の風合いの点から好ましい。なお、低収縮繊維群を構成するポリマーの種類にとくに限定はなく、ポリエステル、レーヨン、ポリアミド等、上記延伸ＰＥＳ繊維（ＩＩＩ）より湿熱収縮率が８％以上小さければよい。
【００３４】
また、該混繊糸において、延伸ＰＥＳ繊維（ＩＩＩ）と低収縮繊維との糸長差は４％以上であることが好ましい。該糸長差が４％未満の場合、該混繊糸を用いた織編物は膨らみ感、ソフト感等の風合に欠けたものとなってしまう。該糸長差は初期の目的に応じて設定すればよく、上限はとくに限定されないが、３０％以下であることが好ましい。
【００３５】
該混繊糸は、通常の紡糸混繊方式、延伸混繊方式、エアー加工混繊方式等により製造され、加工工程、製織編時の糸条通過安定性を得るために、インターレース、タスラン（ヘバライン ファイバー テクノロジー Ｉｎｃ 登録商標）等の空気交絡処理を施していてもよい。また該混繊糸はループ毛羽が形成されていてもよい。
【００３６】
次に芯鞘加工糸への利用について説明する。
上記延伸ＰＥＳ繊維（ＩＩＩ）を芯鞘構造加工糸の芯部分に用いることにより、柔軟で風合に優れたスパンライクな加工糸が得られる。このような芯鞘加工糸は、仮撚による嵩高性を有し、仮撚後の加工糸の解舒性のために、空気絡合による糸間の絡合が糸長方向で特定の間隔で成されていることが望ましい。これによって芯鞘各糸条が集束され、柔軟で風合に優れた加工糸が得られる。空気絡合処理は仮撚加工の前でも後でもよく、所期の目的に応じて決定すればよい。仮撚温度は該加工糸を構成する芯糸および鞘糸のうち、低融点糸の融点以下の温度で行うことが好ましく、仮撚数Ｔは通常のポリエステル加工糸の仮撚数でよく、下記式の範囲内であることが好ましい。
Ｔ＝Ｔ_０｛１５０／〔Ｄ×（Ｒ^１／Ｒ^２）〕｝^１／２
Ｒ^１／Ｒ^２＝ｋ・ｒ
（ただし、１２００≦Ｔ_０≦２８００、０．９≦ｋ≦１．４であり、Ｒ^１は供給糸の供給ローラの速度、Ｒ^２はデリバリーローラの速度、ｒは嵩高糸の製造において用いられる常用のＲ^１とＲ^２の速度比、Ｄは供給糸の繊度（デニール）である。）
【００３７】
芯糸、鞘糸の繊度は用途に応じて選定すべきであるが、一般的に総繊度において鞘糸≧芯糸とすることが好ましい。鞘糸をして用いられる繊維を構成するポリマーとしては、ポリエステルが好ましく、該ポリエステルは変性されていてもよい。またポリエステルとポリアミドとからなる複合繊維を用いることも可能である。
【００３８】
本発明に係わるＰＥＳ（Ｉ）の繊維への利用方法として複合繊維、混合紡績糸がある。
まず、複合繊維について説明する。
ＰＥＳ（Ｉ）を他の繊維形成ポリマーと複合させて繊維化させ、該複合繊維を上述の延伸条件で延伸することにより、複合形態によって２成分の収縮率差による自己捲縮性の発現が見られたり、ＰＥＳ（Ｉ）に伴う高い収縮性に付随して繊維軸方向に繊維形成性ポリマーの細かい皺の発現が見られたり、大きい収縮差による効率良い剥離の発現が見られたりする。このように、天然繊維よりなる布帛の有する伸縮性、張り、腰、膨らみ、ぬめり、しなやかさ、ソフトさ等の優れた特性を発揮することが可能となる。
【００３９】
複合形態としてはサイドバイサイド型、芯鞘型、偏心芯鞘型、多層積層型、放射状型等が挙げれるが、該ＰＥＳ（Ｉ）の高収縮性が発揮でき得る形態であれば、目的に応じて選択することができる。
従来の捲縮付与型の複合繊維としてサイドバイサイド型や偏心芯鞘型で、重合度の異なるポリエチレンテレフタレート同士を複合化した繊維、ポリエチレンテレフタレートとポリブチレンテレフタレートとを複合化した繊維、イソフタル酸、ビスフェノールＡのエチレンオキサイド付加物を共重合したポリエステルとポリエチレンテレフタレートとを複合化した繊維等が挙げられるが、これらの複合繊維は、収縮特性が不十分であったり、たとえ収縮特性が満足できても耐光堅牢度に大きな欠点があった。上述のＰＥＳ（Ｉ）と繊維形成性ポリマーからなる複合繊維は収縮特性を満足する上に耐光性という欠点をも解消したのである。この複合繊維の有する収縮特性を利用して、該複合繊維を一成分とした不織布が有用である。
【００４０】
次に混合紡績糸について説明する。
上述の延伸ＰＥＳ繊維（ＩＩＩ）をステープルファイバーとし他の合成繊維および／または天然繊維と通常の混合紡糸方式で製造された混合紡績糸からなる織編物は、熱処理することにより、延伸ＰＥＳ繊維（ＩＩＩ）からなるステープルファイバーが織編物拘束の下でも十分に収縮するので、該織編物に嵩高性が発現し、また、従来品に比較し耐光性にも優れているため実用性が非常に高いものである。
延伸ＰＥＳ繊維（ＩＩＩ）からなるステープルファイバーならびに、他の合成繊維および／または天繊維の繊度、カット長、撚係数、混紡率はとくに限定されず、所期の目的に応じて適宜設定することができる。
【００４１】
ここまではＰＥＳ（Ｉ），ＰＥＳ繊維（ＩＩ）、延伸ＰＥＳ繊維（ＩＩＩ）を利用した複合繊維、混繊糸、芯鞘加工糸、混合紡績糸について説明したが、本発明はこれら繊維を用いた布帛をも包含するものである。
該布帛としては、織編物、不織布、延伸ＰＥＳ繊維（ＩＩＩ）をグランド糸またはパイル糸としたパイル製品などを挙げることができる。該布帛に含有される上述の延伸ＰＥＳ繊維（ＩＩＩ），複合繊維、混繊糸、混合紡績糸、芯鞘加工糸等は２０重量％以上、好ましくは３０重量％以上である。該含有量が２０重量％未満の場合、布帛の拘束下で、本発明の繊維が十分収縮することができず、目的としたものが得られない。たとえ得られたとしても、その布帛の芯的存在である収縮性の高い繊維が少ないため、張り、腰、反発感、膨らみ等に欠けたものとなってしまう。また該布帛に外力が付与されると、のびたり、へたったりという形態安定性に欠けたものとなってしまう。
該布帛の高収縮性を有する繊維を含んでいるために、従来品が有していた風合不足、耐光性不良という問題点を解消したものが得られ、また、パイル製品では高密度で嵩高いものが得られるようになる。
【００４２】
【実施例】
以下、実施例により本発明を具体的に説明する。
なお、以下の実施例、比較例、参考例における各物性は以下の方法により測定した。
【００４３】
〔構造式（１）で示される化合物の含有量（モル％）〕
重水素化トリフルオロ酢酸を溶媒としてポリエステルの^１Ｈ−ＮＭＲ測定結果に基づき算出した。
【００４４】
〔ポリエステルの固有粘度（ｄｌ／ｇ）〕
フェノ−ル／テトラクロロエタン（等重量比）の混合溶媒を用い、３０℃で測定した。
【００４５】
〔ポリエステルの融点（℃）、ガラス転移点温度（℃）および結晶化度（Ｊ／ｇ）〕Ｄｉｆｆｅｒｅｎｔｉａｌ Ｓｃａｎｎｉｎｇ Ｃａｌｏｒｉｍｅｔｅｒ （メトラ−ＴＡ３０００、パ−キンエルマ−社製）を使用し、試料１０ｍｇ、昇温および降温速度１０℃／分の条件で、窒素置換を行ないながら測定し、同じ試料でこの操作を２回繰り返して２回目の値を実測値とした。また試料に熱処理を施し、十分に結晶化させた後の結晶融解熱（Ｊ／ｇ）を上記装置により測定し結晶化度として示した。
【００４６】
〔ポリエステル繊維の複屈折率〕
ナトリウム光源を用い、偏光顕微鏡の光路にべレックスコペンセーターを挿入し、α−ブロモナフタレン中で測定した値である。
【００４７】
〔ポリエステル繊維の乾熱収縮率（Ｄｓｒ：％）〕
初荷重１ｍｇ／ｄ下で試料に５０ｃｍ間隔の印をつけ、ついで試料を１８０℃に昇温された乾熱雰囲気中に５ｍｇ／ｄの荷重下１０分間放置し、その後取り出して１ｍｇ／ｄの荷重下で印の間隔Ｌｃｍを測定し、次式により算出した。
乾熱収縮率（Ｄｓｒ：％）＝〔（５０−Ｌ）／５０〕×１００
【００４８】
〔ポリエステル繊維の乾熱収縮応力（ｍｇ／ｄ）〕
オ−トグラフに２０ｃｍのヤ−ンを取り付け、５０ｍｇ／ｄの初荷重をかけた後、１℃／分の昇温速度で昇温し、収縮により発現する力を測定した。
【００４９】
〔ポリエステル繊維の湿熱収縮率（Ｗｓｒ：％）〕
初荷重１ｍｇ／ｄ下で試料に５０ｃｍ間隔の印をつけ、ついで試料を９８℃の熱水中に５ｍｇ／ｄの荷重下３０分間放置し、その後取り出して１ｍｇ／ｄの荷重下で印の間隔Ｌ´ｃｍを測定し、次式により算出した。
湿熱収縮率（Ｗｓｒ：％）＝〔（５０−Ｌ´）／５０〕×１００
【００５０】
〔混繊糸の湿熱収縮率（Ｗｓｒ′：％）〕
上述のポリエステル繊維の湿熱収縮率の測定と同様の方法で測定して求めた。
【００５１】
〔混繊糸を構成する各繊維の湿熱収縮率差（ΔＷ％）〕
混繊糸を構成する繊維群を分別した後、上述の沸水収縮率の測定方法にしたがってそれぞれの沸水収縮率を求め、その差で示した。
【００５２】
〔混繊糸の糸長差（ｌ％）〕
混繊糸の５０ｃｍ間隔で印をつけ、混繊糸を構成する繊維群を分別した後、それぞれの繊維群に１ｍｇ／ｄの荷重をかけた状態でその間隔ｌ_１、ｌ_２を測定し、その差で示した。
【００５３】
〔耐光堅牢度〕
下記の染色条件で染色されたサンプルにつきＪＩＳ Ｌ０８４２−１９８８に準拠して測定した。

【００５４】
〔布帛の深色度（Ｋ／Ｓ）〕
サンプル布の分光反射率（Ｒ）をカラ−アナライザ−（自動記録式分光光度計、日立製作所製）で測定し、下記式ク−ベルカ−ムンク（Ｋｕｂｅｌｋａ−Ｍｕｎｋ）の式から求めた。この値が大きい程深色度が大であることを示す。なお、サンプル布は上記の染色条件において染料濃度が３．０％で染色したものを用いた。
Ｋ／Ｓ＝（１−Ｒ）^２／２Ｒ
（Ｒはサンプル布の可視部反射率曲線の最大吸収波長位置における反射率である。）
【００５５】
〔布帛の風合、伸縮性の評価〕
サンプル布の膨らみ、ソフト感、張り、腰、きしみ感の風合、伸縮性を一対比較による官能評価を行った。
【００５６】
〔参考例Ａ〕
ノルボルナン２，３−ジメタノール（表１に示される化合物）を４．２モル％、エチレングリコール９５．８モル％からなるジオール原料とテレフタル酸とから、ジオール原料：テレフタル酸＝１．２：１となるように調整してスラリーを形成し、このスラリーを加圧下（絶対圧２．５ｋｇ／ｃｍ^２）、温度２５０℃でエステル化率が９５％になるまでエステル化反応を行い、低重合体を製造した。次に触媒として３５０ｐｐｍの三酸化アンチモンを添加し、絶対圧１ｔｏｒｒの減圧下に２８０℃で１．５時間低重合体を重縮合し、固有粘度が０．６５ｄｌ／ｇのポリエステルを得た。このポリエステルをノズルからストランド状に押し出して切断し、直径２．８ｍｍ、長さ３．２ｍｍの円柱状チップを得た。
得られたポリエステルチップをＭＮＲにより解析したところ、ノルボルナン２，３−ジメタノールが全ジカルボン酸成分に対して、５モル％共重合されているポリエステルであることが確認された。また、該ポリエステルチップのＴｇは７８℃、Ｔｍは２４１℃、結晶化処理後の結晶融解熱は３６Ｊ／ｇであった。
【００５７】
〔参考例Ｂ〜Ｑ〕
表１に示された化合物を用いて、また表１に示される共重合量にする以外は参考例Ａと同様にしてポリエステルを製造し、ポリエステルチップを得た。各々のポリエステルについて、固有粘度、Ｔｇ、Ｔｍ、結晶化融解熱を測定し表１に示す。
【００５８】
【表１】

【００５９】
〔参考例ａ〜ｑ〕
固有粘度が０．７０ｄｌ／ｇのポリエチレンテレフタレート（参考例ａ）、表２に示された化合物を用いて、また表２に示される共重合量にする以外は参考例Ａと同様にしてポリエステルを製造し、ポリエステルチップを得た。各々のポリエステルについて固有粘度、Ｔｇ、Ｔｍ、結晶化融解熱を測定し表２に示す。
【００６０】
【表２】

【００６１】
【表３】

【００６２】
〔参考例１〕
参考例Ａで得られたポリエステルチップを押し出し機にて溶融押し出しし、２９０℃で０．２５φ×２４ホールの丸孔ノズルから吐出し、１０００ｍ／分で巻き取った。ついで８５℃のホットプレート、１００℃（参考例１−１）、１２０℃（参考例１−２）のホットプレートを用い、５００ｍ／分の速度で延伸を行い、７５デニール／２４フィラメントのマルチフィラメントを得た。延伸倍率はそれぞれ３．２０倍であり、切断延伸倍率の０．７５倍であった。
これらのマルチフィラメントの諸物性を表に示す。
ノルボルナン２，３−ジメタノールを特定量共重合したポリエステルからなり繊維は高い乾熱収縮率、湿熱収縮率を有しながら、乾熱収縮応力も高いものであった。
また、これらのマルチフィラメントを編地のグランド糸として使用し、立毛編物を試作したところ、毛羽密度が高く、高級感のある編地であった。さらに、該編地に上述の染色条件で染色を施したところ、複屈折率が低く、それに起因した深色度が高い編物であり、耐光堅牢度も５級と良好で全く問題がなかった。
【００６３】
【表４】

【００６４】
〔比較参考例１〕
参考例ａで得られたポリエチレンテレフタレートを用いて、参考例１と同様にして紡糸・延伸を行い、７５デニール／２４フィラメントのマルチフィラメントを得た。
このマルチフィラメントの諸物性を測定し、表に示す。
参考例１で得られた繊維に比較し乾熱収縮応力は同等であったが、乾熱収縮率、湿熱収縮率が極端に低いものであった。
また、これらのマルチフィラメントを編地のグランド糸として使用し、立毛編物を試作したところ、毛羽密度が疎で高級感に欠けたものであった。さらに参考例１と同様にして該編物に染色を施したところ、耐光堅牢度は５級と高いものであったが、複屈折率が高く、深色性の低いものであった。
【００６５】
【表５】

【００６６】
〔参考例２〜１７〕
参考例Ｂ〜Ｑで得られたポリエステルチップを用い、参考例１と同様にして、紡糸・延伸を行い、７５デニール／２４フィラメントのマルチフィラメントを得た。得られた各マルチフィラメントの諸物性を表に示す。比較参考例１で得られた繊維と同等の高い乾熱収縮応力を有していながら、高い乾熱収縮率、湿熱収縮率をも有していた。ついで、参考例１と同様にして該マルチフィラメントをグランド糸とした編地を作成し、染色を施したが、各マルチフィラメントの低複屈折率に起因した高い深色性を示すとともに、耐光堅牢度も問題がなく、実用性の非常に高いものであった。
【００６７】
〔比較参考例２〜７〕
参考例ａ〜ｇで得られたポリエステルチップを用い、参考例１と同様にして紡糸・延伸を行い、７５デニール／２４フィラメントのマルチフィラメントを得た。得られた各マルチフィラメントの諸物性を表に示す。比較参考例１で得られた繊維と同等の高い乾熱収縮応力を有してはいるが、乾熱収縮率、湿熱収縮率が低く、各マルチフィラメントをグランド糸とした編地は毛羽密度が疎で高級感に欠けたものであった。
【００６８】
〔比較参考例８〜１３〕
参考例ｈ〜ｍで得られたポリエステルチップを用い、参考例１と同様にして紡糸・延伸を行おうとしたが、ポリエステルが非晶性であるため、延伸時に糸切れが多発し、満足な延伸糸が得られなかった。
【００６９】
〔比較参考例１４〕
参考例ｎで得られたポリエステルチップを用い、参考例１と同様にして紡糸・延伸を行い、７５デニール／２４フィラメントのマルチフィラメントを得た。得られた各マルチフィラメントの諸物性を表に示す。乾熱収縮率および湿熱収縮率は参考例で得られたマルチフィラメントと同じレベルであったが、乾熱収縮応力が非常に低かった。このマルチフィラメントをグランド糸とした編物は収縮応力が低いために十分な収縮が得られず、毛羽密度が疎で高級感に欠けるものであった。
【００７０】
〔比較参考例１５〜１７〕
参考例ｏ〜ｑで得られたポリエステルチップを用い、参考例１と同様にして紡糸・延伸を行い、７５デニール／２４フィラメントのマルチフィラメントを得た。得られた各マルチフィラメントの諸物性を表に示す。乾熱収縮率、乾熱収縮応力、湿熱収縮率ともに参考例で得られたマルチフィラメントと同じレベルであったが、参考例１と同様にして編地を作製して染色を施し耐光堅牢度を測定したところ、１〜２級と低く、実用的ではなかった。
【００７１】
〔参考例１８〕
高収縮繊維群として参考例１−１で得られたマルチフィラメントを用い、低収縮繊維群として比較参考例１−２のマルチフィラメントを用いて流体処理装置によりエアー圧５ｋｇ／ｃｍ^２で処理して２個／インチの交絡を付与した混繊糸を巻き取った。該混繊糸を構成する繊維群の湿熱収縮率差ΔＷ％は１５％、該混繊糸の湿熱収縮率Ｗｓｒ′％は２０％、糸長差は１０％であった。
該混繊糸に３００Ｔ／Ｍの撚を加えて、経緯使用で製織を行い、通常の加工工程により染色仕上げまでを施し、ツイル織物を作製した。
該ツイル織物の官能評価の結果、膨らみ感、ソフト感、張り、腰、きしみ感は全て良好であり、優れた風合を有するものであった。また該織物は深色性にも優れ、耐光堅牢性も良好であった。
【００７２】
〔比較参考例１８〕
高収縮繊維群として、比較参考例２−１で得られたマルチフィラメントを用いる以外は参考例１８と同様にして混繊糸を作製した。該混繊糸を構成する繊維群の湿熱収縮率差ΔＷ％は４％、該混繊糸の湿熱収縮率Ｗｓｒ′％は１２％、糸長差は２％であった。
該混繊糸に３００Ｔ／Ｍの撚を加えて、経緯使用で製織を行い、通常の加工工程により染色仕上げまでを施し、ツイル織物を作製した。
該ツイル織物の官能評価の結果、膨らみ感、ソフト感が非常に欠けており、風合の悪いものであった。
【００７３】
〔比較参考例１９〕
高収縮繊維群として比較参考例１６−１で得られたマルチフィラメントを用いる以外は参考例１８と同様にして混繊糸を作製した。該混繊糸を構成する繊維群の湿熱収縮率差ΔＷ％は４％、該混繊糸の湿熱収縮率Ｗｓｒ′％は１２％、糸長差は２％であった。
該混繊糸に３００Ｔ／Ｍの撚を加えて、経緯使用で製織を行い、通常の加工工程により染色仕上げまでを施し、ツイル織物を作製した。
該ツイル織物の官能評価の結果、膨らみ感、ソフト感が非常に欠けており、風合の悪いものであった。
【００７４】
〔参考例１９〕
高収縮繊維群として参考例１−１で得られたマルチフィラメントを用い、低収縮繊維群として比較参考例１−２のマルチフィラメントを用いて流体処理装置によりエアー圧５ｋｇ／ｃｍ^２で処理して２個／インチの交絡を付与した後、仮撚温度１８０℃、仮撚数２０００Ｔ／Ｍの仮撚を行い、芯鞘加工糸を得た。
この糸に３００Ｔ／Ｍの撚を加えて、経緯使用で製織を行い、通常の加工工程により染色仕上げまでを施し、ツイル織物を作製した。該織物を構成する芯鞘加工糸の芯糸と鞘糸の糸長差は８％であった。
該ツイル織物の官能評価の結果、膨らみ感、ソフト感、張り、腰、きしみ感は全て良好であり、優れた風合を有するものであった。また該織物は深色性にも優れ、耐光堅牢性も良好であった。
【００７５】
〔比較参考例２０〕
高収縮繊維群として比較参考例２−１で得られたマルチフィラメントを用い、仮撚温度を２００℃とする以外は参考例１９と同様にして芯鞘加工糸を得た。
該加工糸を用いて参考例１９と同様にしてツイル織物を作製した。該織物を構成する芯鞘加工糸の芯糸と鞘糸の糸長差は２％であった。該糸長差が２％であるため、すなわち高収縮繊維群として用いたマルチフィラメントの収縮率が小さいために織物としての風合が欠けたものであった。
【００７６】
〔比較参考例２１〕
高収縮繊維群として比較参考例１６−１で得られたマルチフィラメントを用い、仮撚温度を２００℃とする以外は参考例１９と同様にして芯鞘加工糸を得た。該加工糸を用いて参考例１９と同様してツイル織物を作製した。該織物を構成する芯鞘加工糸の芯糸と鞘糸の糸長差は７％であった。
該織物の風合は参考例１９と同様に良好であったが、耐光堅牢性が１〜２級であり、非常に悪いものであった。
【００７７】
〔実施例１〕
参考例Ａで得られたポリエステルチップと、参考例ａで得られたポリエステルチップをサイドバイサイド型の複合形態となるようにして紡糸を行い、ついで参考例１と同様にして延伸を行い、７５デニール／２４フィラメントの複合マルチフィラメントを得た。
該複合繊維に３００Ｔ／Ｍの撚を加えて、経緯使用で製織を行い、通常の加工工程より染色仕上げまでを施し、ツイル織物を作製した。
得られた織物を構成する繊維は、その繊維を構成するポリエステルの収縮率差により、加工工程中きめ細かいスパイラル状の捲縮を発現し、織物としては適度な伸縮性を有しており、ウール織物と同等の膨らみ、張り、腰、反発感を有していた。さらに染色による深色性にも優れ、また耐光堅牢度も良好で実用に耐えられるものであった。
また、上記のサイドバイサイド型複合繊維を５１ｍｍに切断したステープルファイバーを用いて抄紙法で不織布を作製した。該不織布は加工工程中の熱処理によりきめの細かい捲縮が発現し、伸縮性に富んだものであった。さらに該不織布は染色による深色性に優れ、耐光堅牢度も良好であった。
【００７８】
〔比較例１〕
実施例１において、参考例Ａで得られたポリエステルチップに代えて、参考例ｂで得られたポリエステルチップを用いる以外は実施例１と同様にして複合マルチフィラメントを得た。ついで該複合マルチフィラメントを用いて実施例１と同様にしてツイル織物を作製し、官能評価を行った。
得られた織物を構成する繊維は、その繊維を構成するポリエステルの収縮率差が小さいため、きめの細かい捲縮の発現が少なく、織物としての伸縮性、膨らみ、張り、腰、反発感に欠けていた。
【００７９】
〔比較例２〕
実施例１において、参考例Ａで得られたポリエステルチップに代えて、参考例ｐで得られたポリエステルチップを用いる以外は実施例１と同様にして複合マルチフィラメントを得た。ついで該複合マルチフィラメントを用いて実施例１と同様にしてツイル織物を作製し、官能評価を行った。
得られた織物は伸縮性、風合に優れたものであったが、耐光堅牢度が１〜２級と低く、耐光性に非常に劣るものであった。
【００８０】
〔実施例２〕
実施例１で得られた複合繊維を５１ｍｍに切断したステープルファイバーと、繊度が１デニール、カット長５１ｍｍのポリエチレンテレフタレートステープルファイバーとを用いて、５０：５０の重量比で混合紡績糸を作製した。この混合紡績糸を経緯使いで製織を行い、通常の加工工程により染色仕上げまでを施し、ツイル織物を作製した。
得られた織物は加工工程中の熱処理により、複合ステープルファイバーにきめの細かい捲縮が発現しており、織物として適度な伸縮性を有していた。また、ポリエチレンテレフタレートステープルファイバーが織物表面にループ、毛羽として位置することにより、ウール織物と同等の膨らみ、張り、腰、反発感をも有していた。さらに染色による深色性に優れ、耐光堅牢度も良好であった。
【００８１】
産業上の利用可能性
本発明の繊維は、染色性、深色性に優れているのみならず、高収縮率、高い収縮応力特性をも有し、しかも耐光性、染色堅牢度に非常に優れており、かかる繊維単独使用のみならず、かかる繊維を一成分した混繊糸、芯鞘加工糸、混合紡績糸としても有用である。、また本発明の繊維を構成するポリエステルを一成分とした複合繊維はきめの細かい捲縮が発現するので、かかる複合繊維を一部用いることにより伸縮性に富んだ布帛が得られる。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a conjugate fiber containing, as a component, a polyester excellent in dyeability, deep colorability and light fastness.
[0002]
[Prior art]
Polyester fibers represented by polyethylene terephthalate fibers are widely used because they have many excellent properties, but natural fibers such as wool and silk, and semi-synthetic fibers such as rayon and acetate. Compared with the fiber, there is a disadvantage that the color clarity and depth, particularly the black color depth and the color developing property, are inferior.
Such drawbacks are that the polyester fiber is usually dyed with a disperse dye having poor clarity, and that the refractive index of the polyester fiber (the refractive index in the direction perpendicular to the fiber axis) is 1.7 and other fibers. And the reflectance of light on the fiber surface increases, resulting in an increase in the intensity of white reflection and scattering from the surface of the cloth made of polyester fibers.
[0003]
As a solution to these problems, various modifications have been proposed to introduce a dyeing seat having excellent clarity such as a cationic dye or an acid dye into the polyester fiber.However, although the clarity of the color is improved, The light reflection scattering caused by the high refractive index of the polyester-based fiber does not decrease, and the effect of improving the color depth is essentially not exhibited.
[0004]
On the other hand, it has been proposed that the surface of the polyester fiber is coated with a compound having a low refractive index to improve the deep coloration and increase the depth of the color. Compounds and the like have been proposed (Japanese Patent Publication No. 2-42938).
Also, a method has been proposed in which fine irregularities having a pitch smaller than the wavelength of light are formed on the surface of a polyester fiber to suppress the reflection and scattering of light on the fiber surface (Japanese Patent Publication No. 62-20304, JP-B-62-28229).
[0005]
However, fibers obtained by a method of coating a polyester fiber surface with a compound having a low refractive index have poor durability of the coating against dry cleaning, and even if a sufficient dark color effect can be achieved, wind is not sufficient. In this case, problems such as a decrease in color fastness of the dyed product and a decrease in light fastness occur.
Furthermore, in the method of forming fine irregularities on the fiber surface, during the post-processing step, the irregularities are damaged and the effect of suppressing the reflection and scattering of light on the fiber surface is reduced, and the appearance is reduced due to the effects of wear when worn. Failure may occur.
[0006]
In addition, there is a high shrink yarn as one method of using polyester fibers. As a method of using such a high shrink yarn, (1) a method of combining a high shrink yarn and a low shrink yarn, causing a difference in yarn length by heat treatment, and giving the fabric a swelling feeling, and (2) a simple method of using the high shrink yarn. A yarn having a large denier, a low shrinkage yarn and a single yarn having a small denier are used in combination, and the heat treatment causes a difference in yarn length, and the single yarn with a small denier disposed on the surface of the fabric. The method of using the gentleness of the surface touch on the fabric by using a single-denier large yarn placed on the core of the yarn to make the fabric stretch and waist. (3) Used as a ground yarn for pile knitting and napped products And (4) a method of using a high-shrinkage polymer as a component of the composite spinning to form a latent crimped yarn, (5) a method of integrally molding and three-dimensional molding There are ways to do that.
[0007]
As a method for producing such a high shrinkage yarn, conventionally, it has been generally practiced to copolymerize isophthalic acid as a polymerization component when polymerizing polyester to modify the acid component. This is presumably because the method of modifying the acid component facilitates separation and recovery of the glycol component in the polymerization step. However, in order to obtain a high shrinkage fiber by modifying the acid component, the copolymerization amount of the copolymer component must be increased, thereby deteriorating the excellent performance inherent in the polyester. There is.
[0008]
Therefore, recently, not only the acid component such as isophthalic acid but also the glycol component has been modified. Among them, the most common are polyesters obtained by copolymerizing an alkylene oxide adduct of bisphenol A and polyesters obtained by copolymerizing an alkylene oxide adduct of bisphenol A with isophthalic acid. These polyesters exhibit high shrinkage performance with a smaller amount of copolymerization compared to modification of only the acid component, and impart high shrinkage and high shrinkage stress characteristics while maintaining the inherent performance of polyester It is effective as a means to do it.
However, polyesters obtained by copolymerizing a polyalkylene oxide adduct of bisphenol A have problems that light resistance and dyeing fastness are very poor.
[0009]
Further, as another means for obtaining a high shrinkage fiber, there is a method of lowering the heat treatment temperature of the drawn yarn of the polyester fiber to lower the crystallinity of the polyester. Although this method can provide a highly shrinkable yarn, the stress during dry heat shrinkage is reduced, and another method of obtaining a high shrinkage yarn is to lower the heat treatment temperature during the drawing of the polyester fiber to reduce the crystallinity. There is a way to lower. Although this method can provide a highly shrinkable yarn, the stress during dry heat shrinkage is reduced, and only a high shrinkage yarn having a small heat shrinkage stress can be obtained. Therefore, when a yarn such as a combination of high-shrinkage fibers and low-shrinkage fibers is mixed into a fabric such as a woven or knitted fabric, the effect of high shrinkage is hardly exhibited.
[0010]
The present invention has been studied to obtain fibers having excellent shrinkage and high shrinkage stress characteristics in addition to excellent dyeability and deep-colored properties, by copolymerizing a compound having a specific chemical structure with a specific amount of polyester, It was found that a fiber that satisfies the dyeability, deep color, and shrinkage characteristics was obtained.
A polyester obtained by copolymerizing a compound having a specific chemical structure in an amount of 5 to 100 mol% is disclosed in US DEFENSIVE PUBLICATION T896033, but it has been difficult to convert the polyester into a fiber.
The present invention can be fiberized by copolymerizing a specific amount of the compound having the specific chemical structure, and the obtained fiber is not only excellent in dyeability and deep color, but also has high shrinkage. -It has been found that it has high shrinkage stress characteristics and is also extremely excellent in light resistance and color fastness.
[0011]
[Problems to be solved by the invention]
The object of the present invention is to use a polyester which is not only excellent in dyeability and deep color, but also has high shrinkage and high shrinkage stress characteristics, and furthermore has excellent light fastness and dyeing fastness as one component. It is to provide a composite fiber.
[0012]
[Means for Solving the Problems]
The present invention provides a fiber [hereinafter, referred to as PES fiber (II)] comprising a polyester [hereinafter, referred to as PES (I)] obtained by copolymerizing a compound represented by the following structural formula (1) at 2 to 20 mol%. It is.
[0013]
Embedded image

[0014]
The present invention is a composite fiber containing PES (I) as one component.
[0015]
The present invention is a hetero-shrinkage mixed fiber comprising PES fiber (II) as one component.
[0016]
The present invention is a mixed spun yarn containing staples composed of PES fibers (I) as one component.
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
In the compound represented by the structural formula (1) contained in the PES (I), examples of the ester-forming functional group include a hydroxy group, a hydroxyalkyl group, a carboxyl group, and an ester-forming derivative thereof. The alkyl constituting the hydroxyalkyl group is not limited, but is preferably an alkyl having 1 to 4 carbon atoms, such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group, and may be a branched alkyl. The ester-forming derivative of a carboxyl group is preferably an alkyl having 1 to 4 carbon atoms such as a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a carboxybutyl group.
It is necessary that the compound has one or two ester-forming functional groups, and the copolymerization in the polyester molecular chain results in high shrinkage properties as a polyester fiber, It is preferable from the point of view, and it is preferable that the number of ester-forming functional groups is two. In that case, the ester-forming functional groups may be of the same type or of different types.
[0018]
In addition, a hydrogen atom and an alkyl group are bonded to carbons other than the ester-forming functional group bonded in the compound, except that the ester-forming functional group is bonded in that the polymerizable property is not inhibited. It is preferable that a hydrogen atom is bonded to carbon. In addition, as an alkyl group, a C1-C5 alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, is mentioned, and this group may be branched.
[0019]
Such compounds include norbornane 2,3-dimethanol, norbornane 2,3-diethanol, norbornane 2,3-dicarboxylic acid, norbornane 2,3-dicarboxylic acid dimethyl ester, norbornane 2,3-dicarboxylic acid diethyl ester, Hydrodimethanonaphthalenediethanol, perhydrodimethanonaphthalenediethanol, perhydrodimethanonaphthalenedicarboxylic acid, dimethyl perhydrodimethanonaphthalenedicarboxylate, tricyclodecanedimethanol, tricyclodecanediethanol, tricyclodecanedicarboxylic acid, tricyclodecanedicarboxylic acid Cyclodecanedicarboxylic acid dimethyl ester, tricyclodecanedicarboxylic acid diethyl ester and the like, and in these compounds other than the ester-forming functional group is bonded Compounds in which an alkyl group is bonded to oxygen can be mentioned. Further, as the compound other than the alkyl group, a compound to which another substituent such as a sulfonyl group is bonded is also included in the present invention. Among the above-mentioned compounds, norbornane 2,3-dimethanol, norbornane 2,3-dicarboxylic acid, norbornane 2,3-dicarboxylic acid dimethyl ester, perhydrodimethanonaphthalene in terms of polymerizability, thread formability, fiber strength, and shrinkability. Preferred are dimethanol, perhydrodimethanonaphthalenedicarboxylic acid, dimethyl perhydrodimethanonaphthalenedicarboxylate, tricyclodecane dimethanol, tricyclodecanediethanol, tricyclodecanedicarboxylic acid, and dimethyl tricyclodecanedicarboxylate. Further, from the viewpoint of the polymerizability, norbornane 2,3-dimethanol, norbornane 2,3-dicarboxylic acid, norbornane 2,3-dicarboxylic acid dimethyl ester, perhydrodimethanonaphthalenediethanol, perhydrodimethanonaphthalenedicarboxylic acid In the dimethyl perhydrodimethanonaphthalenedicarboxylate, it is preferable that two ester-forming functional groups are located at the trans position.
[0020]
The polyester in the present invention is a polyester containing terephthalic acid as a main dicarboxylic acid component and at least one alkylene glycol selected from ethylene glycol, trimethylene glycol and tetramethylene glycol as a main glycol component. Further, a third component other than the compound represented by the structural formula (1) may be copolymerized within a range not to impair the object of the present invention.
Examples of the third component include isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, and 4,4'-diphenylsulfonedicarboxylic acid. 4,4'-diphenylisopropylidene dicarboxylic acid, 1,2-diphenoxyethane-4 ', 4 "-dicarboxylic acid, anthracene dicarboxylic acid, 2,5-pyridine dicarboxylic acid, diphenoxy ketone dicarboxylic acid, 5-sodium Aromatic dicarboxylic acids such as sulfoisophthalic acid, dimethyl-5-sodium sulfoisophthalate, 5-tetrabutylphosphonium sulfoisophthalic acid; aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid; decalin Dicarboxylic acid, shik Alicyclic dicarboxylic acids such as hexanedicarboxylic acid; hydroxycarboxylic acids such as β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, hydroxypropionic acid and hydroxyacrylic acid; carboxylic acids derived from their ester-forming derivatives; aliphatic lactones such as ε-caprolactone; aliphatic diols such as hexamethylene glycol, neopentyl glycol, diethylene glycol and polyethylene glycol; hydroquinone catechol, naphthalenediol, resorcinol, bispheno And aromatic diols such as ethylene oxide adduct of bisphenol A, bisphenol A and ethylene oxide of bisphenol S; and aliphatic diols such as cyclohexane dimethanol. These third components are only one kind. Other 2 kinds or more may be copolymerized.
[0021]
In the PES (I) of the present invention, a polycarboxylic acid such as trimellitic acid, trimesic acid, pyromellitic acid, tricarballylic acid or the like; glycerin, trimethylolethane, trimethyloyl, etc., within a range where the polyester is substantially linear. -Polyhydric alcohols such as propane and pentaerythritol may be copolymerized.
[0022]
The content of the compound represented by the structural formula (1) is in the range of 2 to 20 mol%, preferably 3 to 18 mol%, based on the dicarboxylic acid component constituting the polyester. If the content is less than 2 mol%, the desired fiber cannot be obtained because the degree of crystallinity of the polyester is insufficiently reduced and the shrinkage of the fiber is insufficiently increased. On the other hand, when the content exceeds 20 mol%, the polymerizability of the polyester is reduced, and it is difficult to obtain a crystalline polyester. Even if it is obtained, the melting point of the polyester is lowered, which is required for the polyester fiber. It does not satisfy the heat resistance.
Further, as the content of the compound increases, the crystallinity and melting point of the polyester decrease, but the shrinkage rate of the polyester fiber tends to increase. The content may be changed within the scope of the present invention in consideration of properties and the like.
The polyester according to the present invention can be polymerized by a usual method. For example, direct esterification of terephthalic acid and alkylene glycol, transesterification of lower alkyl ester of terephthalic acid such as dimethyl terephthalate with alkylene glycol, or reaction of terephthalic acid with alkylene oxide Reaction in the first step to form an alkylene glycol ester of terephthalic acid and / or a low polymer thereof, and polymerizing the reaction product obtained in the first step with antimony trioxide, germanium oxide, tetraalkoxyethane, etc. It is produced by a second-stage reaction in which a polycondensation reaction is carried out under reduced pressure at 230 to 300 ° C. using a catalyst until the desired degree of polymerization is reached. At that time, a desired amount of the compound represented by the structural formula (1) is added to an arbitrary stage until the completion of the polycondensation reaction, for example, to a starting material of the polyester, or after the transesterification reaction and before the polycondensation reaction. be able to.
Further, in order to increase the degree of polymerization of the polyester, it is also possible to carry out solid phase polymerization after conducting polymerization in a liquid phase.
[0023]
The PES (I) of the present invention preferably has an intrinsic viscosity (measured at 30 ° C. using a mixed solvent of phenol / tetrachloroethane (weight ratio: 50/50)) of 0.4 to 1.5. . When the intrinsic viscosity of the PES (I) is less than 0.4, the fiber strength and shrinkage characteristics when fiberized become insufficient, and the intended purpose is hardly achieved. On the other hand, if the intrinsic viscosity of the PES (I) exceeds 1.5, the melt viscosity of the polyester becomes too high, and the spinnability such as spinning and drawing deteriorates.
[0024]
The PES (I) of the present invention may contain, if necessary, an antioxidant, an ultraviolet absorber, a fluorescent brightener, a matting agent, an antistatic agent, a flame retardant, a flame retardant auxiliary within a range not to impair the present invention. And additives such as lubricants, colorants, plasticizers, and inorganic fillers.
[0025]
PES fiber (II) can be easily fiberized by a general melt spinning method. The obtained spun yarn may be drawn by a usual method, and can be drawn under the usual polyester fiber drawing conditions. Stretching is performed by preheating with a heating roller, stretching at a stretching ratio according to the speed of the winding roller, and performing heat treatment. Further, it may be stretched by a method in which spinning stretching is directly connected, such as spin draw, and then heat-treated.
[0026]
The cross-section of the PES fiber (II) can be any cross-sectional shape such as circular, polylobal such as trilobal to octahedral, T-shaped, V-shaped, flat, and rectangular, The fibers are not limited to solid fibers, and may be hollow fibers or porous fibers. The thickness (fineness) of the fiber is not particularly limited, and can be any thickness (fineness) according to the intended purpose. Further, the PES fiber (II) may have unevenness in the fiber axis direction.
Further, the PES fiber (II) can be used not only as a filament but also as a staple fiber.
[0027]
The PES fiber (I) thus obtained has a birefringence Δn satisfying the following expression (2).
−5.55 × A + 80 ≦ Δn × 10³≦ −5.55 × A + 165 (2)
[However, A is the content (mol%) of the compound represented by the structural formula (1). ]
When the birefringence Δn is within such a range, the polyester fiber is excellent in dyeability and deep color when dyed.
[0028]
Further, when the compound represented by the structural formula (1) is contained in the molecular chain of the polyester, the aliphatic cyclic skeleton of the compound is positioned as a side chain with respect to the molecular chain. Even if the content of the compound is low, the amorphousness increases, the lowering of the secondary transition temperature is suppressed, and when the fiber shrinks due to heat, the stress at the time of relaxation inside the fiber is accumulated, so that the shrinkage is high. In addition, the fiber is excellent in heat resistance, color fastness and light fastness. Such light fastness can be expressed as light fastness to a carbon arc lamp, and the above-mentioned PES fiber (II) is quaternary or higher. The dyeing conditions at this time are not particularly limited, and are effective for fibers dyed from a light color to a dark color with any disperse dye, cationic dye, or acid dye.
[0029]
The PES fiber (II) can have not only a high shrinkage rate but also a high shrinkage stress depending on drawing conditions.
In general, fibers having a high shrinkage have a low shrinkage stress, but the polyester fibers of the present invention have both a high shrinkage and a high shrinkage stress depending on the drawing conditions.
That is, the polyester fiber spun by a general melt spinning method is subjected to stretching once after being wound or without being wound, and is stretched by hot stretching. It is preferable to preheat with a heating roller at a temperature of about 75 to 95 ° C. before being supplied to the stretching zone. The film is stretched at a temperature of 150 ° C. or lower, preferably 140 ° C. or lower, at a draw ratio of 0.68 times or more, preferably 0.70 times or more of the cutting stretch ratio. When the stretching temperature exceeds 150 ° C., the shrinkage decreases, and when the stretching ratio is less than 0.68 times the cut stretching ratio, not only a fiber having sufficient heat shrinkage stress is not obtained, but also the residual elongation is too large. It is difficult to use as a clothing fiber.
[0030]
The drawn polyester fiber obtained by drawing in this manner (hereinafter referred to as drawn PES fiber (III)) has a dry heat shrinkage at 180 ° C. of 20% or more, a dry heat maximum shrinkage stress of 250 mg / d or more, And it has a high shrinkage rate and a high shrinkage stress of 98% or more at a heat and heat shrinkage rate of 15% or more. By simultaneously satisfying the three factors of dry heat shrinkage, dry heat maximum shrinkage stress, and wet heat shrinkage, when used as a core filament of a core-sheath processed yarn described later or as a component of a different shrinkage mixed fiber, Thus, a fabric such as a woven or knitted fabric having an appropriate tension, resilience, and swelling can be obtained by post-processing.
When the dry heat shrinkage at 180 ° C. is less than 20%, the stretched PES fiber (II) is used as a core filament of a core-sheath processed yarn described later, and the one formed in a woven or knitted fabric does not exhibit sufficient shrinkage. , Bulkiness tends to be unsatisfactory. The upper limit of the dry heat shrinkage is not particularly limited, but is preferably 80% or less in consideration of the deterioration of the yarn quality. In particular, it is more preferably in the range of 20 to 75%.
When the wet heat shrinkage at 98 ° C. is less than 15%, the difference from the above-mentioned dry heat shrinkage becomes large. The shrinkage in dry heat treatment such as heat setting after wet heat treatment such as water treatment or dyeing is too large, so that it tends to lack shape stability and shape homogeneity. The upper limit of the wet heat shrinkage is not particularly limited, but is preferably 75% or less in consideration of fiber physical properties, particularly sagging of a woven or knitted fabric. In particular, it is more preferably in the range of 15 to 70%. The difference between the dry heat shrinkage and the wet heat shrinkage is not particularly limited, but is preferably in the range of 1 to 30% for the above-described reason.
Furthermore, since the shrinkage stress affects the ease with which the constrained yarn or woven or knitted fabric shrinks, the larger the shrinkage stress, the more easily the shrinkage occurs even under the constraint. If the maximum dry heat shrinkage stress at 180 ° C. is 250 mg / d or more, the resin shrinks sufficiently even under constraint.
[0031]
As a method of using the drawn PES fiber (III), there are a different shrinkage mixed fiber and a core / sheath processed yarn.
First, the application to the different shrinkage mixed fiber will be described.
2. Description of the Related Art Conventionally, different shrinkage blended yarns made of polyethylene terephthalate fibers having different shrinkage rates have been used mainly in women's dresses, blouses, and the like for silk-like woven and knitted fabrics having a high softness and drape. Such a mixed yarn is obtained by mixing drawn yarns having different boiling water shrinkage ratios and drawing and mixing undrawn yarns having the same physical properties under different heat treatment conditions. However, these methods merely provide a mixed yarn with a difference in boiling water shrinkage, and the heat shrinkage difference becomes smaller than the initial due to the heat history up to weaving and knitting. Since the stress accumulated due to the difference in the heat shrinkage rate in the weaving and knitting restraint is small, the feeling is poor.
When the above-mentioned stretched PES fiber (III) is used as the high shrinkage fiber in such a conventional different shrinkage mixed fiber, the above-mentioned problem is solved, and practical performance such as light resistance is greatly improved.
The different shrinkage mixed fiber yarns are obtained by mixing the above drawn PES fiber (III) as a high shrinkage fiber group and a fiber having a lower shrinkage ratio than the drawn PES fiber (III) as a low shrinkage fiber group. It is entangled or mixed spun. The difference between the high heat shrinkage fiber group and the low shrinkage fiber group at 98 ° C. (hereinafter simply referred to as wet heat shrinkage) is preferably 8% or more. If the wet heat shrinkage difference is less than 8%, it is difficult to obtain a sufficient heat shrinkage behavior in a process after forming the woven or knitted fabric. That is, in order to form a specific structure in which the high shrinkage fiber group is arranged in the core after the woven or knitted fabric and the low shrinkage fiber group is arranged in the sheath portion, the high shrinkage fiber group and the low shrinkage fiber group It is not enough to use only the difference in the wet heat shrinkage of the woven or knitted fabric as a guide. After that, sufficient heat shrinkage behavior is caused in the process after the heat treatment, and the texture such as tension, waist, and swelling is improved.
In order to cause a sufficient heat shrinkage behavior in the process after forming the woven or knitted fabric, the difference in wet heat shrinkage between the high shrinkage fiber group and the low shrinkage fiber group should be in the range of 8 to 60%, especially 10 to 55%. preferable.
[0032]
Further, such a different shrinkage mixed fiber preferably has a wet heat shrinkage of 10 to 55%, particularly preferably 10 to 50%. When the wet heat shrinkage ratio is less than 10%, the feeling of tension, waist, swelling and the like when formed into a woven or knitted fabric is insufficient, while when it exceeds 55%, the thermal stability of the mixed fiber may be poor. is there.
[0033]
Further, the fineness of each fiber of the high shrinkage fiber group constituting the mixed fiber, that is, the drawn PES fiber (III), is preferably 1 to 10 denier, and the single fiber fineness of the low shrinkage fiber group is preferably 5 denier or less. The weight ratio between the shrinkable fiber group and the low shrinkage fiber group is preferably in the range of former: latter = 2: 1 to 1: 5 from the viewpoint of the texture of the woven or knitted fabric. The type of the polymer constituting the low shrinkage fiber group is not particularly limited, and it is sufficient that the wet heat shrinkage of the drawn PES fiber (III), such as polyester, rayon, and polyamide, is 8% or less.
[0034]
Further, in the mixed fiber, the difference in yarn length between the drawn PES fiber (III) and the low shrinkage fiber is preferably 4% or more. If the yarn length difference is less than 4%, the woven or knitted fabric using the mixed yarn lacks a feeling such as a swelling feeling and a soft feeling. The yarn length difference may be set according to the initial purpose, and the upper limit is not particularly limited, but is preferably 30% or less.
[0035]
The mixed yarn is manufactured by a normal spinning and mixing method, a drawing and mixing method, an air-processing and mixing method, and the like. An air entanglement treatment such as Fiber Technology Inc (registered trademark) may be performed. Further, the mixed fiber may have a loop fluff.
[0036]
Next, application to a core-sheath processing yarn will be described.
By using the above-mentioned drawn PES fiber (III) for the core portion of the core-sheath structured processed yarn, a spun-like processed yarn having flexibility and excellent feeling can be obtained. Such a core-sheath processed yarn has bulkiness due to false twisting, and due to unwinding of the processed yarn after false twisting, entanglement between yarns due to air entanglement occurs at a specific interval in the yarn length direction. It is desirable that this is done. As a result, each core-sheath yarn is bundled, and a processed yarn excellent in softness and feel is obtained. The air entanglement treatment may be performed before or after false twisting, and may be determined according to the intended purpose. The false twisting temperature is preferably performed at a temperature equal to or lower than the melting point of the low melting point yarn of the core yarn and the sheath yarn constituting the processed yarn, and the number of false twists T may be the number of false twists of a normal polyester processed yarn. It is preferably within the range of the formula.
T = T₀｛150 / [D × (R¹/ R²)]｝^1/2
R¹/ R²= Kr
(However, 1200 ≦ T₀≦ 2800, 0.9 ≦ k ≦ 1.4, and R¹Is the speed of the supply roller of the supply yarn, R²Is the speed of the delivery roller, and r is the usual R used in the production of bulky yarn.¹And R²Is the fineness (denier) of the supply yarn. )
[0037]
The fineness of the core yarn and the sheath yarn should be selected according to the application, but it is generally preferable that the sheath yarn is equal to or greater than the core yarn in the total fineness. As the polymer constituting the fiber used as the sheath yarn, polyester is preferable, and the polyester may be modified. It is also possible to use a composite fiber composed of polyester and polyamide.
[0038]
As a method of using PES (I) for fibers according to the present invention, there are a conjugate fiber and a mixed spun yarn.
First, the conjugate fiber will be described.
PES (I) is combined with another fiber-forming polymer to form a fiber, and the composite fiber is drawn under the above-mentioned drawing conditions. In addition, fine wrinkles of the fiber-forming polymer appear in the fiber axis direction accompanying the high shrinkage associated with PES (I), and efficient peeling occurs due to a large difference in shrinkage. As described above, it is possible to exhibit excellent properties such as elasticity, tension, waist, swelling, sliminess, flexibility, and softness of a fabric made of natural fibers.
[0039]
Examples of the composite form include a side-by-side type, a core-sheath type, an eccentric core-sheath type, a multilayer lamination type, a radial type, and the like, as long as the PES (I) can exhibit high shrinkage depending on the purpose. You can choose.
Conventional crimp-giving composite fibers of side-by-side type or eccentric core-sheath type, fibers obtained by compounding polyethylene terephthalates with different degrees of polymerization, fibers obtained by compounding polyethylene terephthalate and polybutylene terephthalate, isophthalic acid, bisphenol A Fibers obtained by compounding a polyester obtained by copolymerizing an ethylene oxide adduct with polyethylene terephthalate, and the like. These composite fibers have insufficient shrinkage characteristics, and are light-fast even if shrinkage characteristics can be satisfied. Every time there was a major drawback. The composite fiber comprising PES (I) and the fiber-forming polymer described above satisfies the shrinkage characteristics and eliminates the disadvantage of light resistance. Utilizing the shrinkage property of the composite fiber, a nonwoven fabric containing the composite fiber as a component is useful.
[0040]
Next, the mixed spun yarn will be described.
A woven or knitted fabric comprising a mixed spun yarn produced by using the above-mentioned drawn PES fiber (III) as a staple fiber and other synthetic fibers and / or natural fibers by a usual mixed spinning method is subjected to a heat treatment to obtain a drawn PES fiber (III). ), The staple fiber shrinks sufficiently even under the constraint of the woven or knitted fabric, so that the woven or knitted fabric expresses bulkiness, and has a very high light resistance as compared with the conventional product, so that it is very practical. It is.
The fineness, cut length, twist coefficient, and blending ratio of the staple fiber made of the drawn PES fiber (III) and other synthetic fibers and / or heavenly fibers are not particularly limited, and can be appropriately set according to the intended purpose. it can.
[0041]
So far, composite fibers, mixed fibers, core-sheath processed yarns, and mixed spun yarns using PES (I), PES fibers (II) and drawn PES fibers (III) have been described, but the present invention uses these fibers. It also includes the cloth that has been mixed.
Examples of the fabric include a woven or knitted fabric, a nonwoven fabric, and a pile product in which the drawn PES fiber (III) is a ground yarn or a pile yarn. The content of the above-mentioned stretched PES fiber (III), conjugate fiber, mixed fiber, mixed spun yarn, core-sheath processed yarn and the like contained in the fabric is 20% by weight or more, preferably 30% by weight or more. If the content is less than 20% by weight, the fibers of the present invention cannot sufficiently shrink under the constraint of the fabric, and the desired product cannot be obtained. Even if it is obtained, the fiber lacks high shrinkage, which is the core of the fabric, and thus lacks tension, waist, resilience, swelling, and the like. Further, when an external force is applied to the fabric, the fabric lacks form stability such as stretching or sagging.
Since the fabric contains fibers having a high shrinkage property, it is possible to solve the problem of insufficient feeling and poor light fastness of the conventional products, and it is possible to obtain high density and bulk in pile products. Higher things can be obtained.
[0042]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
In addition, each physical property in the following Examples, Comparative Examples, and Reference Examples was measured by the following methods.
[0043]
[Content (mol%) of the compound represented by the structural formula (1)]
Polyester with deuterated trifluoroacetic acid as solvent¹It was calculated based on the H-NMR measurement results.
[0044]
[Intrinsic viscosity of polyester (dl / g)]
It measured at 30 degreeC using the mixed solvent of phenol / tetrachloroethane (equal weight ratio).
[0045]
[Melting Point (° C.), Glass Transition Temperature (° C.), and Crystallinity (J / g) of Polyester] Using a Differential Scanning Calorimeter (Metra-TA3000, manufactured by Perkin Elmer), 10 mg of a sample, heating and The measurement was carried out under the condition of a temperature lowering rate of 10 ° C./min while performing nitrogen replacement, and this operation was repeated twice with the same sample, and the second value was used as the actually measured value. The heat of crystal fusion (J / g) after the sample was subjected to heat treatment and sufficiently crystallized was measured by the above apparatus, and was shown as the degree of crystallinity.
[0046]
(Birefringence of polyester fiber)
It is a value measured in α-bromonaphthalene using a sodium light source with a Belex copen sweater inserted in the optical path of a polarizing microscope.
[0047]
[Dry heat shrinkage of polyester fiber (Dsr:%)]
The sample is marked at intervals of 50 cm under an initial load of 1 mg / d, and then left in a dry heat atmosphere heated to 180 ° C. under a load of 5 mg / d for 10 minutes. The distance Lcm between the marks was measured below and calculated by the following equation.
Dry heat shrinkage (Dsr:%) = [(50−L) / 50] × 100
[0048]
[Dry heat shrinkage stress of polyester fiber (mg / d)]
A 20 cm yarn was attached to the autograph, an initial load of 50 mg / d was applied, the temperature was raised at a rate of 1 ° C./min, and the force generated by shrinkage was measured.
[0049]
[Wet heat shrinkage of polyester fiber (Wsr:%)]
The sample is marked at intervals of 50 cm under an initial load of 1 mg / d, then the sample is left in 98 ° C. hot water under a load of 5 mg / d for 30 minutes, then taken out, and the mark is removed under a load of 1 mg / d. L'cm was measured and calculated by the following equation.
Wet heat shrinkage (Wsr:%) = [(50−L ′) / 50] × 100
[0050]
[Heat and heat shrinkage of mixed fiber (Wsr ':%)]
It was determined by measuring in the same manner as the above-described measurement of the wet heat shrinkage of the polyester fiber.
[0051]
[Wet heat shrinkage difference (ΔW%) of each fiber constituting the mixed fiber]
After the fiber group constituting the mixed fiber was separated, each boiling water shrinkage was determined according to the above-described method of measuring the boiling water shrinkage, and the difference was shown.
[0052]
[Yarn length difference (l%) of mixed fiber]
Marks are made at 50 cm intervals between the mixed yarns, and the fiber groups constituting the mixed yarns are separated. Then, a load of 1 mg / d is applied to each of the fiber groups, and the interval 1 is applied.₁, L₂Was measured and indicated by the difference.
[0053]
(Light fastness)
It measured based on JIS L0842-1988 about the sample dyed on the following dyeing conditions.

[0054]
[Deepness of fabric (K / S)]
The spectral reflectance (R) of the sample cloth was measured with a color analyzer (automatic recording type spectrophotometer, manufactured by Hitachi, Ltd.), and determined from the following equation Kubelka-Munk. The greater this value, the greater the deep chromaticity. The sample cloth used was dyed at a dye concentration of 3.0% under the above dyeing conditions.
K / S = (1-R)²/ 2R
(R is the reflectance at the position of the maximum absorption wavelength in the reflectance curve of the visible portion of the sample cloth.)
[0055]
[Evaluation of texture and elasticity of fabric]
The swelling, softness, tension, waist, texture of the squeaky feeling, and elasticity of the sample cloth were subjected to a sensory evaluation by pairwise comparison.
[0056]
[Reference Example A]
From a diol raw material composed of 4.2 mol% of norbornane 2,3-dimethanol (compound shown in Table 1) and 95.8 mol% of ethylene glycol and terephthalic acid, a diol raw material: terephthalic acid = 1.2: 1. To form a slurry, and press the slurry under pressure (2.5 kg / cm absolute pressure).²), An esterification reaction was carried out at a temperature of 250 ° C. until the esterification ratio reached 95% to produce a low polymer. Next, 350 ppm of antimony trioxide was added as a catalyst, and the low polymer was polycondensed at 280 ° C. for 1.5 hours under reduced pressure of 1 torr to obtain a polyester having an intrinsic viscosity of 0.65 dl / g. The polyester was extruded from a nozzle into a strand and cut to obtain a columnar chip having a diameter of 2.8 mm and a length of 3.2 mm.
When the obtained polyester chip was analyzed by MNR, it was confirmed that norbornane 2,3-dimethanol was a polyester in which 5 mol% was copolymerized with respect to all dicarboxylic acid components. The polyester chip had a Tg of 78 ° C., a Tm of 241 ° C., and a heat of crystal fusion after crystallization treatment of 36 J / g.
[0057]
[Reference Examples B to Q]
A polyester was produced in the same manner as in Reference Example A except that the compounds shown in Table 1 were used and the copolymerization amounts were changed to those shown in Table 1, to obtain polyester chips. For each polyester, the intrinsic viscosity, Tg, Tm, and heat of fusion of crystallization were measured and are shown in Table 1.
[0058]
[Table 1]

[0059]
[Reference Examples a to q]
Polyester terephthalate having an intrinsic viscosity of 0.70 dl / g (Reference Example a) and a compound shown in Table 2 were used. Manufacture and a polyester chip were obtained. The intrinsic viscosity, Tg, Tm and heat of crystallization of each polyester were measured and are shown in Table 2.
[0060]
[Table 2]

[0061]
[Table 3]

[0062]
[Reference Example 1]
The polyester chip obtained in Reference Example A was melt-extruded with an extruder, discharged at 290 ° C. from a 0.25φ × 24-hole round nozzle, and wound up at 1000 m / min. Then, using a hot plate at 85 ° C., a hot plate at 100 ° C. (Reference Example 1-1), and a hot plate at 120 ° C. (Reference Example 1-2), drawing was performed at a speed of 500 m / min to obtain a multifilament of 75 denier / 24 filaments. Got. The stretching ratio was 3.20 times, and 0.75 times the cutting stretching ratio.
The properties of these multifilaments are shown in the table.
The fiber made of a polyester obtained by copolymerizing a specific amount of norbornane 2,3-dimethanol had a high dry heat shrinkage, a high wet heat shrinkage, and a high dry heat shrinkage stress.
In addition, when these multifilaments were used as ground yarns of a knitted fabric and a nappi knit was trial-produced, the knitted fabric had a high fluff density and high quality. Further, when the knitted fabric was dyed under the above-described dyeing conditions, the knitted fabric had a low birefringence and a high deep chromaticity due to the low birefringence.
[0063]
[Table 4]

[0064]
[Comparative Reference Example 1]
Using the polyethylene terephthalate obtained in Reference Example a, spinning and drawing were performed in the same manner as in Reference Example 1 to obtain a multifilament of 75 denier / 24 filaments.
Various physical properties of the multifilament were measured and are shown in the table.
Although the dry heat shrinkage stress was equal to that of the fiber obtained in Reference Example 1, the dry heat shrinkage and the wet heat shrinkage were extremely low.
In addition, when these multifilaments were used as ground yarns of a knitted fabric and a trial knitted nap was produced, the fluff density was low and the sense of quality was lacking. Further, when the knitted fabric was dyed in the same manner as in Reference Example 1, the light fastness was as high as 5th grade, but the birefringence was high and the deep color was low.
[0065]
[Table 5]

[0066]
[Reference Examples 2 to 17]
Using the polyester chips obtained in Reference Examples B to Q, spinning and drawing were performed in the same manner as in Reference Example 1 to obtain a multifilament of 75 denier / 24 filaments. Various physical properties of the obtained multifilaments are shown in the table. While having high dry heat shrinkage stress equivalent to that of the fiber obtained in Comparative Reference Example 1, it also had high dry heat shrinkage and wet heat shrinkage. Next, a knitted fabric using the multifilament as a ground yarn was prepared and dyed in the same manner as in Reference Example 1. The multifilament exhibited high deep color due to the low birefringence of each multifilament, and was light-fast. There was no problem at all, and the practicality was very high.
[0067]
[Comparative Reference Examples 2 to 7]
Using the polyester chips obtained in Reference Examples a to g, spinning and drawing were performed in the same manner as in Reference Example 1 to obtain a multifilament of 75 denier / 24 filaments. Various physical properties of the obtained multifilaments are shown in the table. Although having a high dry heat shrinkage stress equivalent to the fiber obtained in Comparative Reference Example 1, the dry heat shrinkage and wet heat shrinkage are low, and the knitted fabric using each multifilament as a ground yarn has a fuzz density. It was sparse and lacked a sense of luxury.
[0068]
[Comparative Reference Examples 8 to 13]
Using the polyester chips obtained in Reference Examples h to m, spinning and drawing were attempted in the same manner as in Reference Example 1. However, since the polyester was amorphous, thread breakage frequently occurred during drawing, and satisfactory drawing was performed. No yarn was obtained.
[0069]
[Comparative Reference Example 14]
Using the polyester chip obtained in Reference Example n, spinning and drawing were performed in the same manner as in Reference Example 1 to obtain a multifilament of 75 denier / 24 filaments. Various physical properties of the obtained multifilaments are shown in the table. The dry heat shrinkage and the wet heat shrinkage were at the same level as the multifilament obtained in Reference Example, but the dry heat shrinkage stress was very low. The knitted fabric using the multifilament as the ground yarn did not have sufficient shrinkage due to low shrinkage stress, and had a low fuzz density and lacked a sense of quality.
[0070]
[Comparative Reference Examples 15 to 17]
Using the polyester chips obtained in Reference Examples o to q, spinning and drawing were performed in the same manner as in Reference Example 1 to obtain multifilaments of 75 denier / 24 filaments. Various physical properties of the obtained multifilaments are shown in the table. The dry heat shrinkage, the dry heat shrinkage stress, and the wet heat shrinkage were at the same level as the multifilament obtained in Reference Example, but a knitted fabric was prepared and dyed in the same manner as in Reference Example 1 to obtain light fastness. As a result of measurement, it was as low as 1st and 2nd grades and was not practical.
[0071]
[Reference Example 18]
Using the multifilament obtained in Reference Example 1-1 as the high-shrink fiber group and using the multifilament of Comparative Reference Example 1-2 as the low-shrink fiber group, air pressure of 5 kg / cm by a fluid treatment device.², And the mixed fiber yarn with 2 / inch entanglement was wound. The wet heat shrinkage difference ΔW% of the fiber group constituting the mixed fiber was 15%, the wet heat shrinkage Wsr ′% of the mixed fiber was 20%, and the yarn length difference was 10%.
A twist of 300 T / M was added to the mixed fiber, weaving was performed using weft, and dyeing and finishing were performed by a normal processing step to produce a twill woven fabric.
As a result of the sensory evaluation of the twill woven fabric, the swelling feeling, the soft feeling, the tension, the waist, and the squeaky feeling were all good, and the feeling was excellent. The woven fabric was also excellent in deep color and light fastness.
[0072]
[Comparative Reference Example 18]
A mixed fiber was produced in the same manner as in Reference Example 18 except that the multifilament obtained in Comparative Reference Example 2-1 was used as the high shrinkage fiber group. The wet heat shrinkage difference ΔW% of the fiber group constituting the mixed fiber was 4%, the wet heat shrinkage Wsr ′% of the mixed fiber was 12%, and the yarn length difference was 2%.
A twist of 300 T / M was added to the mixed fiber, weaving was performed using weft, and dyeing and finishing were performed by a normal processing step to produce a twill woven fabric.
As a result of the sensory evaluation of the twill fabric, it was found that the swelling feeling and the soft feeling were very poor and the feeling was poor.
[0073]
[Comparative Reference Example 19]
A mixed fiber was produced in the same manner as in Reference Example 18 except that the multifilament obtained in Comparative Reference Example 16-1 was used as the high shrinkage fiber group. The wet heat shrinkage difference ΔW% of the fiber group constituting the mixed fiber was 4%, the wet heat shrinkage Wsr ′% of the mixed fiber was 12%, and the yarn length difference was 2%.
A twist of 300 T / M was added to the mixed fiber, weaving was performed using weft, and dyeing and finishing were performed by a normal processing step to produce a twill woven fabric.
As a result of the sensory evaluation of the twill fabric, it was found that the swelling feeling and the soft feeling were very poor and the feeling was poor.
[0074]
[Reference Example 19]
Using the multifilament obtained in Reference Example 1-1 as the high-shrink fiber group and using the multifilament of Comparative Reference Example 1-2 as the low-shrink fiber group, air pressure of 5 kg / cm by a fluid treatment device.²And twisting was performed at a false twist temperature of 180 ° C. and a false twist number of 2000 T / M to obtain a core-sheath processed yarn.
A twist of 300 T / M was added to this yarn, weaving was performed by using the process, and dyeing and finishing were performed by a normal processing process to produce a twill fabric. The yarn length difference between the core yarn and the sheath yarn of the core-sheath processed yarn constituting the woven fabric was 8%.
As a result of the sensory evaluation of the twill woven fabric, the swelling feeling, the soft feeling, the tension, the waist, and the squeaky feeling were all good, and the feeling was excellent. The woven fabric was also excellent in deep color and light fastness.
[0075]
[Comparative Reference Example 20]
A core-sheath processed yarn was obtained in the same manner as in Reference Example 19, except that the multifilament obtained in Comparative Reference Example 2-1 was used as the high shrinkage fiber group, and the false twist temperature was set to 200 ° C.
A twill fabric was produced in the same manner as in Reference Example 19 using the processed yarn. The yarn length difference between the core yarn and the sheath yarn of the core-sheath processing yarn constituting the woven fabric was 2%. Since the yarn length difference was 2%, that is, the shrinkage rate of the multifilament used as the high shrinkage fiber group was small, the hand as a woven fabric was lacking.
[0076]
[Comparative Reference Example 21]
Using the multifilament obtained in Comparative Reference Example 16-1 as a group of high shrinkage fibers, a core-sheath processed yarn was obtained in the same manner as in Reference Example 19 except that the false twist temperature was set to 200 ° C. Using the processed yarn, a twill fabric was produced in the same manner as in Reference Example 19. The yarn length difference between the core yarn and the sheath yarn of the core-sheath processed yarn constituting the woven fabric was 7%.
The hand of the woven fabric was as good as in Reference Example 19, but the light fastness was 1st or 2nd class and was very poor.
[0077]
[Example 1]
The polyester chip obtained in Reference Example A and the polyester chip obtained in Reference Example a were spun so as to form a side-by-side composite form, and then stretched in the same manner as in Reference Example 1 to obtain 75 denier / A composite multifilament of 24 filaments was obtained.
A twist of 300 T / M was added to the conjugate fiber, weaving was performed by using the process, and the processing was performed from a normal processing step to a dyeing finish to produce a twill woven fabric.
The fibers constituting the obtained woven fabric exhibit fine spiral crimps during the processing step due to the difference in shrinkage of the polyester constituting the fibers, and have a moderate elasticity as a woven fabric. Had the same swelling, tension, waist, and resilience. Further, it was excellent in deep color by dyeing, and also had good light fastness and was practically usable.
In addition, a nonwoven fabric was produced by a papermaking method using staple fibers obtained by cutting the above-mentioned side-by-side type composite fibers into 51 mm. The nonwoven fabric exhibited fine crimps due to the heat treatment during the processing step, and had high elasticity. Further, the nonwoven fabric was excellent in deep coloration by dyeing, and also had good light fastness.
[0078]
[Comparative Example 1]
A composite multifilament was obtained in the same manner as in Example 1 except that the polyester chip obtained in Reference Example b was used instead of the polyester chip obtained in Reference Example A. Next, a twill fabric was prepared in the same manner as in Example 1 using the composite multifilament, and the sensory evaluation was performed.
The fibers constituting the obtained woven fabric have a small expression of fine crimps due to a small difference in the shrinkage ratio of the polyester constituting the fibers, and lack the elasticity, swelling, tension, waist, and resilience of the woven fabric. I was
[0079]
[Comparative Example 2]
A composite multifilament was obtained in the same manner as in Example 1, except that the polyester chip obtained in Reference Example p was used instead of the polyester chip obtained in Reference Example A. Next, a twill fabric was prepared in the same manner as in Example 1 using the composite multifilament, and the sensory evaluation was performed.
The obtained woven fabric was excellent in stretchability and feeling, but had low light fastness of 1st to 2nd grades and was extremely poor in light fastness.
[0080]
[Example 2]
Using the staple fiber obtained by cutting the conjugate fiber obtained in Example 1 into 51 mm and the polyethylene terephthalate staple fiber having a fineness of 1 denier and a cut length of 51 mm, a mixed spun yarn was produced at a weight ratio of 50:50. This mixed spun yarn was woven by using weft and subjected to dyeing and finishing by a normal processing step to produce a twill woven fabric.
The resulting woven fabric exhibited fine crimps in the composite staple fiber due to the heat treatment during the processing step, and had appropriate stretchability as the woven fabric. In addition, since the polyethylene terephthalate staple fiber was positioned as a loop or a fluff on the surface of the woven fabric, it had the same swelling, tension, waist, and resilience as the wool woven fabric. Furthermore, it was excellent in deep color by dyeing, and light fastness was also good.
[0081]
Industrial applicability
The fiber of the present invention is not only excellent in dyeability and deep color, but also has a high shrinkage rate and a high shrinkage stress property, and is extremely excellent in light resistance and color fastness. It is useful not only for use but also as a mixed fiber, a core-sheath processed yarn, and a mixed spun yarn containing such a fiber as one component. In addition, since the composite fiber containing the polyester constituting the fiber of the present invention as one component develops a fine crimp, a fabric with high elasticity can be obtained by partially using the composite fiber.

Claims (2)

A composite fiber comprising a polyester obtained by copolymerizing a compound having the following structural formula (1) in an amount of 2 to 20 mol% and a fiber-forming polymer.

(Wherein, R _{1 to} R ₁₀ are groups selected from an ester-forming functional group, a hydrogen atom, and an alkyl group, and one or two of R _{1 to} R ₁₀ are ester-forming functional groups. X is 0 or 1, and y is an integer satisfying 1 ≦ x + y ≦ 3.) The conjugate fiber according to claim 1, wherein a polyester obtained by copolymerizing a compound having the structural formula (1) in an amount of 2 to 20 mol% and a fiber-forming polymer are compounded in a side-by-side type.