JP3804771B2 - Polyketone fiber - Google Patents

Description

【００１５】
ポリケトン中の１−オキソトリメチレンの割合が９５質量％未満では、結晶性が大きく低下し、高強度で高融点を有するポリケトン繊維を得ることができない。１−オキソトリメチレンの割合が高いほど、ポリケトン繊維の強度、弾性率及び融点が高くなる。ポリケトン中の１−オキソトリメチレンの好ましい割合は９７質量％以上、より好ましくは１００質量％である。
ポリケトンの極限粘度は、低くなるにつれて高強度の物性が得られにくくなり、高くなるにつれて溶剤への溶解性、曳糸性及び生産性が低下することから、ポリケトンの極限粘度は、好ましくは１〜２０、より好ましくは３〜１０、最も好ましくは４〜８である。
【００１６】
本発明のポリケトン繊維には、下記の（ａ）〜（ｄ）からなる群より選ばれた少なくとも１種のイオン性化合物が、ポリケトン繊維に対して０．０５〜５質量％付着していることが極めて重要である。
（ａ）Ｒ¹−Ｐ（＝Ｏ）（ＯＸ¹）（ＯＸ²）
（ｂ）Ｒ²−Ｐ（＝Ｏ）（Ｏ−Ｒ³）（ＯＸ³）
（ｃ）Ｒ⁴−Ｓ（＝Ｏ）（ＯＸ⁴）
（ｄ）Ｒ⁵−Ｃ（＝Ｏ）（ＯＸ⁵）
式中、Ｘ¹〜Ｘ⁵は水素、アルカリ金属、アルカリ土類金属、及びＮＨ₄からなる群より選ばれた少なくとも１種、Ｒ¹〜Ｒ⁵は炭素数が３〜３０の有機基である。
【００１７】
本発明のポリケトン繊維に付着している化合物は、イオン性化合物（リン酸化合物、亜リン酸化合物、スルホン酸化合物、カルボン酸化合物）である。イオン性官能基を有さず、エーテル、エステル、ケトン等のノニオン性基のみを有するノニオン性化合物は、十分な制電性が発現しないばかりか、熱延伸時の熱劣化による装置の汚れや強度低下の原因となる。
イオン性化合物の官能基（リン酸基、亜リン酸基、スルホン酸基、カルボン酸基）と結合する基（Ｘ¹〜Ｘ⁵）は、水素、アルカリ金属、アルカリ土類金属、及びＮＨ₄からなる群より選ばれた少なくとも１種であることが必要である。この結合基が炭化水素基等の場合には、制電性及び集束性に優れたポリケトン繊維を製造することが困難となる。この結合基は、ポリケトン繊維の制電性、集束性及び繊維物性の観点からアルカリ金属が好ましく、カリウム及びナトリウムがより好ましい。この結合基は複数種の基が混合して存在していてもよい。
【００１８】
本発明におけるイオン性化合物は、炭素数３〜３０、好ましくは４〜１８の有機基（Ｒ¹〜Ｒ⁵）を有することが必要である。有機基が存在しない場合、又は有機基の炭素数が２以下の場合には、イオン性化合物のポリケトン繊維に対する親和性が低くなり、繊維表面に均一に分散することが困難となる、イオン性化合物の油膜強度が低下する、ポリケトン繊維の耐摩耗性や耐衝撃性が低下する、延伸時、撚糸時、紡績時等に単糸切れや繊維表面のフィブリル化が起こる、といった問題が生じる。炭素数が３０を越える場合には、制電性が不十分となる、フィラメントの集束性が低下する、摩擦抵抗が増大する、延伸時や撚糸時に毛羽やフィブリル化が発生しやすくなる、パッケージからの解舒性やパッケージの巻き取り形態が不均一になる、といった問題が生じる。
【００１９】
有機基の構造には制限はなく、例えば、飽和脂肪族基、不飽和脂肪族基、芳香族基、又はこれらが混合した炭化水素基であってもよく、炭化水素基の一部又は全部がエーテル基、エステル基、ケトン基、水酸基、アミド基、スルホン酸基、リン酸基、カルボン酸基等の基で置換されていてもよい。イオン性化合物の耐熱性の観点からは飽和脂肪族炭化水素基が好ましい。有機基は直鎖状であっても分岐を有するものであってもよい。また、有機基は構造の異なる複数種類の基が混合していてもよく、装置にイオン性化合物の結晶が析出しにくいという観点から、混合物であることが好ましい。
【００２０】
上記の特性を有するイオン性化合物としては、例えば、下記の化合物が挙げられるが、これらに限定されるものではない。
化合物（ａ）及び（ｂ）の例としては、アルキルリン酸エステル（オクチルホスフェートカリウム塩、セチルホスフェートカリウム塩、ステアリルホスフェートカリウム塩、ラウリルホスフェートカリウム塩、パルミチルホスフェートカリウム塩、イソプロピルホスフェートカリウム塩、イソセチルホスフェートカリウム塩、セチルホスフェートナトリウム塩、セチルホスフェートアンモニウム塩等）、アルキルエーテルホスフェート（ポリオキシエチレンセチルエーテルホスフェートカリウム塩、ポリオキシエチレンラウリルエーテルホスフェートナトリウム塩、ポリオキシエチレンステアリルエーテルホスフェートアンモニウム塩等）、アルキルアリルエーテルホスフェート（ノニルフェニルエーテルホスフェートカリウム塩等）等が挙げられる。
【００２１】
化合物（ｃ）の例としては、アルキルアリルスルホネート（ドデシルベンゼンスルホネートナトリウム塩等）、アルキルスルホネート（オクチルスルホネートカリウム塩等）、アルキルナフタレンスルホネート（ジブチルナフタレンスルホネートナトリウム塩、トリイソプロピルナフタレンスルホネートナトリウム塩等）、アルキルスルホサクシネート（ジオクチルスルホサクシネートナトリウム塩等）、アルキルサルフェート（オクチルサルフェートナトリウム塩等）、アルキルエーテルサルフェート（ラウリルエーテルサルフェートナトリウム塩等）、アルキルアリルエーテルサルフェート（ノニルフェニルエーテルサルフェートナトリウム塩等）等が挙げられる。
【００２２】
化合物（ｄ）の例としては、脂肪酸石鹸（ステアリン酸ナトリウム塩）、多価カルボン酸石鹸（ヒマシ油ナトリウム石鹸等）等が挙げられる。
化合物（ａ）〜（ｄ）は、これらを混合して用いてもよい。
本発明において、イオン性化合物は、ポリケトン繊維に対して０．０５〜５質量％付着していることが重要であり、好ましくは０．１〜１質量％である。付着率が０．０５質量％未満では、制電性及び集束性が不十分で、品位及び工程通過性に問題が生じる。一方、５質量％を越える場合、延伸時や加工時に油剤が装置に付着して装置の汚れが激しくなり、場合によっては結晶が析出して断糸の原因となる。
【００２３】
本発明のポリケトン繊維には、上記のイオン性化合物の他に、必要に応じて、ラジカル抑制剤、他のポリマー、艶消し剤、紫外線吸収剤、難燃剤等の添加剤を含んでいてもよい。
本発明のポリケトン繊維には、制電性、集束性、繊維物性を損なわず、工程通過性に悪影響を及ばさない範囲であれば、上記のイオン性化合物以外の油剤成分、防腐剤、酸化防止剤、乳化剤、防錆剤等が付与されていてもよい。使用可能な油剤成分には制限はなく、平滑性向上、集束性補足、制電性補足等、目的に応じて適宜選定することが可能である。
【００２４】
このような化合物としては、例えば、ステアリン酸オクチル、オレイン酸ラウリル等のエステル化合物、パラフィン系、ナフテン系の鉱物油、ポリオレフィンオキシド等のポリエーテル、ポリオキシエチレンステアリルエーテル等のノニオン性界面活性剤、ステアリルアミンメチルスルホン酸塩、オクチルアミンジメチルリン酸塩等のカチオン性化合物等が挙げられる。これら油剤成分の付着量は、多すぎると制電性が損なわれたり、熱延伸時の油剤の熱劣化による繊維物性低下、工程通過性の悪化、撚糸強力利用率の低下等の問題の原因となるため、上記の（ａ）〜（ｄ）のイオン性化合物の総付着量に対して、好ましくは０〜１００質量％、好ましくは０〜５０質量％、最も好ましくは０〜３０質量％である。
【００２５】
本発明のポリケトン繊維は、汎用的に用いられるためには力学物性及び熱特性に優れていることが望まれ、そのためには、発達した結晶構造を有することが求められる。具体的には、本発明のポリケトン繊維の結晶化度は６０％以上、かつ、結晶配向度は９０％以上であることが好ましい。結晶化度は高ければ高いほど、強度、弾性率及び融点が向上するため、より好ましくは７０％以上、最も好ましくは８０％以上である。結晶配向度は高いほど弾性率が高く、力学的寸法安定性に優れるため、より好ましくは９５％以上、最も好ましくは９７％以上である。
【００２６】
本発明のポリケトン繊維は、力学特性として、強度及び弾性率に優れることが望ましく、強度は１２ｃＮ／ｄｔｅｘ以上であることが好ましく、より好ましくは１５ｃＮ／ｄｔｅｘ以上、最も好ましくは１７ｃＮ／ｄｔｅｘ以上である。弾性率は２５０ｃＮ／ｄｔｅｘ以上であることが好ましく、より好ましくは３００ｃＮ／ｄｔｅｘ以上、最も好ましくは３５０ｃＮ／ｄｔｅｘ以上である。
本発明のポリケトン繊維の断面形状はどのような形態であってもよく、目的に応じて、円型、三角型、アルファベットの文字の型等、任意の形状を選定できる。摩擦が小さく、フィブリル化しにくく、単糸膠着が起こりにくい、という点から円型断面が好ましい。
【００２７】
ポリケトン繊維の形態には制限はなく、長繊維及び短繊維のいずれであってもよい。長繊維の場合には、モノフィラメント及びマルチフィラメントのいずれであってもよい。マルチフィラメントの場合のフィラメント数は、好ましくは１００本以上、より好ましくは２００本以上、最も好ましくは３００本以上である。
本発明のポリケトン繊維の単糸繊度には制限はないが、細すぎると紡糸時や延伸時、加工時、使用時等に断糸が起こりやすく、太すぎると紡糸速度を速くすることが困難となるため、好ましくは０．１〜１０ｄｔｅｘ、より好ましくは０．５〜５ｄｔｅｘ、最も好ましくは０．８〜２ｄｔｅｘである。
【００２８】
総繊度は、用途、目的に応じて適宜選定すればよく、例えば、産業資材用途では３００〜７０００ｄｔｅｘ、衣料用途では５０〜１０００ｄｔｅｘが好ましい。本発明のポリケトン繊維は、制電性及び集束性に優れ、特にマルチフィラメントでの工程通過性、取り扱い性及び後加工性に優れており、極めて多数本の繊維状とすることが可能である。特に、トウとして取り扱うことが容易であり、短繊維の製造に極めて適する。トウとは、フィラメントが引き揃えられた、総繊度が１０００ｄｔｅｘ以上の繊維束のことである。短繊維の製造に用いるトウの場合、総繊度は１０００〜１００００００ｄｔｅｘが好ましく、生産性及び取り扱い性の観点から３０００〜３０００００ｄｔｅｘがより好ましい。
【００２９】
本発明のポリケトン繊維は、太繊度のトウとして製造、加工することが容易であり、トウを切断して短繊維として使用するのに適する。短繊維とする場合には、工程通過性及び取り扱い性の観点から平均繊維長は５〜３００ｍｍが好ましい。
本発明のポリケトン繊維を短繊維として用いる場合の好適な用途の一つとして紡績糸が挙げられる。紡績糸に加工するには、カードや牽切ロール等、繊維に摩擦や絞りを加える工程を経るため、繊維の摩擦や摩耗による毛羽やフィブリル状物の発生や、余剰の油剤による装置汚れの問題が起こる。しかし、本発明のポリケトン繊維は、繊維に極く少量の、前記のイオン性化合物を付着せしめることで、制電性及び耐摩耗性が向上するため、このような問題を引き起こすことなく紡績糸に加工することができる。
【００３０】
紡績糸を製造する場合には、紡績糸に付与する上記のイオン性化合物（ａ）〜（ｄ）の割合は０．０５〜１質量％であることが必要であり、好ましくは０．１〜０．３質量％である。付与される割合が０．０５質量％未満では制電性及び耐摩耗性が不十分となり、カードで静電気による繊維の交絡やフィブリル状物の発生等の問題が生じる。一方、１質量％を越えるとカードや牽切ロールへの余剰の油剤の付着が起こり、装置が汚れ、長期の連続運転が困難となる。
【００３１】
紡績糸を構成するポリケトン繊維の平均繊維長は、１０〜２００ｍｍ、好ましくは２０〜１５０ｍｍ、より好ましくは３０〜１００ｍｍである。平均繊維長が１０ｍｍ未満の場合、短繊維間の交絡や摩擦が少なくなり、高強度の紡績糸を得ることが困難となる。一方、平均繊維長が２００ｍｍを越える場合、紡績時、製織時、製編時等における工程通過性が悪くなるばかりか、風合い及び品位のよい紡績糸や織編物を得ることが困難となる。
【００３２】
紡績糸を構成するポリケトン繊維の捲縮度は５〜５０％であることが必要であり、好ましくは１０〜３０％である。捲縮度が小さい場合、ポリケトン繊維間の交絡や摩擦が少なくなって、繊維の引き抜けが起こりやすくなり、結果として高強度の紡績糸を得ることが困難となる。一方、捲縮度が大きすぎると、繊維のたるみやもつれが起こり、紡績時や製織時、製編時の工程通過性が悪くなり、得られる紡績糸や織編物の品位も低いものとなる。
【００３３】
ポリケトン紡績糸は、下記式で示す撚り係数（Ｋ）が３０００〜３００００であることが好ましく、７５００〜１５０００であることがより好ましい。
Ｋ＝Ｙ×Ｄ^0.5（Ｔ／ｍ・ｄｔｅｘ^0.5）
式中、Ｙは１ｍあたりの撚糸数（Ｔ／ｍ）、Ｄは紡績糸の繊度（ｄｔｅｘ）である。
撚り係数（Ｋ）が低すぎると引っ張り方向に対する短繊維間の摩擦抵抗が不十分となり、紡績糸の強度、伸度が不十分となる。また、撚り係数（Ｋ）が高すぎるとポリケトン繊維の撚糸強力利用率が大きく低下し十分な強度の紡績糸を得ることが困難となる。
【００３４】
本発明のポリケトン繊維からなる紡績糸は、紡績糸を構成する繊維の５０質量％以上、紡績糸の強度及びコストの観点から、好ましくは７０質量％以上がポリケトン繊維であれば、ポリケトン繊維以外の繊維を用いた混紡糸であってもよい。混紡する繊維の平均繊維長、捲縮度、イオン性化合物の付着量は、上記の紡績に用いるポリケトン繊維に必要な値の範囲内であることが必要である。ポリケトン繊維と混紡可能な繊維には制限はなく、ビスコースレーヨン、ポリエチレンテレフタレート繊維、ポリトリメチレンテレフタレート繊維、ナイロン６６繊維、ナイロン６繊維、アクリル繊維、アラミド繊維、ポリビニルアルコール繊維等の合成繊維、綿、羊毛、麻、絹等の天然繊維を使用することができる。
【００３５】
本発明のポリケトン繊維は、フィラメントのまま撚糸して撚糸コードとして用いることができる。この場合、撚糸コードに対する上述のイオン性化合物の付着率は０．０５〜５質量％であることが必要であり、好ましくは０．１〜１質量％である。イオン性化合物の付着率が０．０５質量％未満の場合には、撚糸コードを構成する繊維の制電性が不十分で、単糸のほつれやたるみが生じる。一方、５質量％を越える場合には、過剰のイオン性化合物がガイドやロールに析出し、糸の汚れや単糸切れを起こし易くなる。
【００３６】
撚糸を行う場合の、下記式で表す撚り係数（Ｋ）は１０００〜３００００でり、好ましくは５５００〜１５０００である。
Ｋ＝Ｙ×Ｄ^0.5（Ｔ／ｍ・ｄｔｅｘ^0.5）
式中、Ｙは１ｍあたりの撚り数（Ｔ／ｍ）、Ｄは撚糸に用いたポリケトン繊維の総繊度（ｄｔｅｘ）である。
撚り係数（Ｋ）が１０００未満になると、撚糸コードの伸度、タフネスが不十分で、曲げや圧縮に対する耐疲労性が不十分となる。また、撚り係数（Ｋ）が３００００を越えると、撚糸強力利用率が大幅に低下し、十分な強度の撚糸コードを得ることが困難となる。
この撚糸コードに、レゾルシン−ホルマリン−ラテックス（ＲＦＬ）等の樹脂を付着させた処理コードは、ゴムとの接着性が高く、タイヤ、ベルト、ホース等のゴム補強材料として有用である。
【００３７】
次に、本発明のポリケトン繊維の製造方法について説明する。
本発明のポリケトン繊維は、公知の湿式紡糸法（ポリケトンを溶剤に溶解した後に凝固浴中で凝固する）により繊維状とし、脱溶剤、乾燥を経て熱延伸を行うことによって製造する方法が好ましく用いられる。高強度のポリケトン繊維を、生産性よく、工業的に製造するには、金属塩溶液を溶剤とする湿式紡糸法がより好ましい。
【００３８】
以下、金属塩溶液を溶剤とする湿式紡糸法を例に説明する。
ポリケトンをハロゲン化亜鉛、ハロゲン化アルカリ金属、ハロゲン化アルカリ土類金属、チオシアン酸アルカリ金属、チオシアン酸アルカリ土類金属等を含有する溶液（例えば、塩化亜鉛／塩化カルシウム水溶液、塩化亜鉛／塩化カルシウム／チオシアン酸カルシウム水溶液）に溶解する。溶解した溶液を、紡糸口金より水等の液体中に吐出して糸条とした後、塩酸等の酸水溶液により金属塩を洗浄除去する。次いで、１００〜２５０℃で乾燥を行い、繊維中に残存する水等の液体をポリケトン繊維に対して１０質量％以下、好ましくは１質量％以下まで除去する。
【００３９】
乾燥は、（乾燥後の糸長／乾燥前の糸長）の比で表される乾燥倍率を０．７〜３倍とすることが好ましく、０．８〜１．５倍がより好ましい。
乾燥された糸（以下、乾燥糸、という）を、引き続き、熱を加えて延伸する。熱延伸倍率は、高いほど高強度で高弾性率のポリケトン繊維が得られることから、好ましくは５倍以上、より好ましくは１０倍以上、最も好ましくは１５倍以上である。延伸段数は１段であってもよいが、１０倍以上の高倍率の延伸を行う場合には２段以上の多段延伸が好ましい。延伸温度は１５０〜２８０℃が好ましく、より好ましくは２２０〜２７５℃である。多段延伸を行う場合には、延伸段数が進むにつれて延伸温度を徐々に高くする、昇温型の熱延伸を行うことが好ましい。必要に応じて、熱延伸終了後のポリケトン繊維を１００〜２８０℃に加熱し、張力０．００１〜１ｃＮ／ｄｔｅｘで熱処理を行い、ポリケトン繊維の熱収縮を抑制することが好ましい。
【００４０】
上記（ａ）〜（ｄ）のイオン性化合物は、乾燥、熱延伸及び熱処理工程のいずれかの段階で付与することが好ましく、特に、熱延伸前のいずれかの工程でイオン性化合物の付与を行い、熱延伸時のポリケトン繊維の制電性及び集束性を向上させることが好ましい。
イオン性化合物の付与は多段階で行ってもよく、例えば、多段延伸において、まず熱延伸前、次に、熱延伸途中の２段階で付与してもよい。ポリケトン繊維に対するイオン性化合物の付着率は、０．０５〜５質量％であることが必要であり、好ましくは０．１〜１質量％である。付着率が０．０５質量％未満では、延伸時の制電性及び集束性が不十分で、毛羽やフィブリル化が起こりやすくなり、工程通過性及び製品品位に悪影響を及ぼす。一方、付着率が５質量％を越える場合、装置汚れ、特に、ガイドやロールの汚れが激しくなり、長期連続運転が困難となる。
【００４１】
イオン性化合物はどのような形態で付与してもよく、ストレート、水溶液、水分散液等、任意の形態で使用することができる。イオン性化合物を付与する方法としては、スプレー法、ローラー給油法、計量ポンプを用いたガイド給油法等、公知の方法をそのまま用いることができる。
このように得られたポリケトン延伸糸に、必要に応じて仕上げ剤を付与する。仕上げ剤の組成は用途、目的に応じて随時選定し、ポリケトン繊維に耐撚糸性、ゴム、樹脂、セメント等との接着性を向上させ、耐熱性を付与することができる。
【００４２】
本発明のポリケトン繊維を紡績糸として用いる場合には、ポリケトン繊維に捲縮を付与し、短繊維に切断する。紡糸から紡績までのいずれかの工程でポリケトン繊維に捲縮を付与することができるが、延伸性や得られる繊維物性の点から延伸終了後に捲縮を付与することが好ましい。捲縮を付与する方法には制限はなく、スタフィンボックス等を用いて加熱下で加圧屈曲させる方法や、延伸終了後の歪みを有するフィラメントを切断後無緊張下で熱処理する方法等の機械的、熱的、化学的な処理を施すことができる。安定した捲縮を付与するために、好ましくは１１０〜２７０℃、より好ましくは１５０〜２５０℃の加熱下で処理する。
【００４３】
ポリケトンフィラメントを短繊維に切断し、紡績する方法としては、直紡、パーロック法、コンバータ法、ステープラ法等の公知に方法を適用することができる。切断の方式は、カッターで定長に切断する方法でも、牽切により短繊維長が分布を有するようにして切断してもよい。また、フィラメントを加熱して熱延伸を行い、引き続き、短繊維に牽切する方法でもよい。牽切法により切断する際には、平均繊維長が５〜３００ｍｍとなるよう、ドラフト比及び牽切張力を設定することが重要である。
【００４４】
牽切により得られたポリケトンスライバーを、粗紡、精紡工程を通して紡績糸とする。紡績時の加撚の方法については制限はなく、用途、目的に応じて、双糸、３子糸等の公知の撚り糸とすることができる。必要に応じて、ポリエステル繊維やポリアミド繊維、セルロース繊維、アラミド繊維、ポリベンザゾール繊維、ポリビニルアルコール繊維、アクリル繊維、ポリエチレン繊維、ポリプロピレン繊維等のポリケトン繊維以外の繊維と混紡して用いてもよい。混紡比率については制限はないが、紡績糸の強度及びコストの観点から、紡績糸中のポリケトン繊維の割合が、好ましくは５０〜１００質量％、より好ましくは７０〜１００質量％である。撚糸数にも制限はないが、撚糸数が多すぎると撚りに伴なう強力低下が起こり、撚糸数が少ないと引き抜けによる強力低下が起こるため、撚糸は上記の撚り係数（Ｋ）が１００〜３０００の範囲で行うことが好ましく、より好ましくは３００〜１０００である。得られる紡績糸の品位、工程通過性の観点から、撚糸張力は０．０１〜０．１ｃＮ／ｄｔｅｘが好ましく、より好ましくは０．０３〜０．０７ｃＮ／ｄｔｅｘである。
【００４５】
本発明のポリケトン繊維を撚糸コードとして使用する場合、撚糸の種類、方法、合撚本数については制限はなく、片撚り糸、もろ撚り糸、ピッコもろ撚り糸、強撚糸など任意の方法が採用され、撚糸に用いる繊維の本数も１本撚り、２本撚り等、特に制限はなく、３本以上であってもよい。撚糸数も用途、使用環境に応じて任意に撚糸数を選定すればよいが、撚り係数（Ｋ）が１０００〜３００００の範囲が好ましく、より好ましくは５５００〜１５０００である。この際、得られる撚糸コードの品位、取り扱い性の観点から、撚糸張力を、下撚り／上撚り共に０．０１〜０．２ｃＮ／ｄｔｅｘとすることが好ましい。
【００４６】
【発明の実施の形態】
本発明を実施例等により具体的に説明するが、これらは本発明の範囲を限定するものではない。
本発明に用いられる各測定値の測定方法は、次の通りである。
（１）極限粘度
極限粘度［η］は、次の定義式に基づいて求める。

定義式中のｔ及びＴは、純度９８％以上のヘキサフルオロイソプロパノール及びヘキサフルオロイソプロパノールに溶解したポリケトンの希釈溶液の２５℃での粘度管の流過時間である。Ｃは上記１００ｍｌ中のグラム単位による溶質重量値である。
【００４７】
（２）繊維の強度、弾性率
繊維の強伸度は、ＪＩＳ−Ｌ−１０１３に準じて測定する。
（３）イオン性化合物及び油剤の付着量
繊維を１０５℃で５時間乾燥し、重量（Ｗ）を秤量する。繊維を４０℃の温水で洗浄後、２５℃のエチルエーテルで洗浄し、繊維表面に付着したイオン性化合物を除去する。エチルエーテルを留去した後に、繊維を１０５℃で５時間乾燥し、重量（Ｗ₀）を秤量し、以下の式から付着率を求める。
イオン性化合物付着率＝［（Ｗ−Ｗ₀）／Ｗ₀］×１００（％）
油剤についても同様の手法で求める。
【００４８】
（４）結晶化度
パーキンエルマー（株）製の示差熱測定装置Ｐｙｒｉｓ１（商標）を用いて、下記条件で測定を行う。サンプルは糸長を５ｍｍにカットした繊維を用いる。
サンプル質量： １ｍｇ
測定温度 ： ３０℃→３００℃
昇温速度 ： ２０℃／分
雰囲気 ： 窒素、流量＝２００ｍＬ／分
得られる吸発熱曲線において、２００〜３００℃の範囲に観測される最大の吸熱ピークの面積から計算される熱量ΔＨ（Ｊ／ｇ）より、下記式から結晶化度を算出する。
結晶化度 ＝ （ΔＨ／２２５） × １００ （％）
【００４９】
（５）結晶配向度
（株）リガク製イメージングプレートＸ線回折装置ＲＩＮＴ２０００（商標）を用いて下記の条件で繊維の回折像を取り込む。
Ｘ線源 ： ＣｕＫα線
出力 ： ４０ＫＶ １５２ｍＡ
カメラ長 ： ９４．５ｍｍ
測定時間 ： ３分
得られた画像の２θ＝２１°付近に観察される（１１０）面を円周方向にスキャンして得られる強度分布の半値幅Ｈから、下記式により結晶配向度を算出する。
結晶配向度＝［（１８０−Ｈ）／１８０］×１００ （％）
【００５０】
（６）平均繊維長
ＪＩＳ−Ｌ−１０１５−７．４．１（Ａ法）に基づいて測定する。
（７）捲縮度
ＪＩＳ−Ｌ−１０１５−７．１２．２に基づいて測定する。
（８）延伸性
５時間の延伸時間内で、断糸や延伸ロールやガイドへの単糸巻き付きの回数を計測し、以下の基準で延伸性を評価する。
○：断糸、単糸巻き付きが１度も発生しない
△：断糸はないが、単糸巻き付きが発生する
×：断糸する
【００５１】
（９）毛羽
巻き取ったパッケージの表面を外観検査し、毛羽の個数を計測する。
○：毛羽が観察されない
△：１〜５ヶの毛羽が観察される
×：毛羽が６ヶ以上観察される
（１０）集束性
パッケージから糸を１ｍ／分の速度で引き出し、引き出されたフィラメントの集束状態を以下の基準で判定する。
○：単糸のばらけがない（１本のフィラメント束である）
△：静電気によりフィラメントが２〜５本の糸に分かれる
×：静電気によりフィラメントが６本以上の糸に分かれる
（１１）ゴム接着力
天然ゴム７０質量％、ＳＢＲ１５質量％、カーボンブラック１５質量％配合の未加硫ゴムを用い、これにポリケトンコードを１ｃｍ埋め込み、１５５℃、３．５ＭＰａ、３０分の条件で加硫後、Ｔ引き抜き強力（Ｎ）を、クロスヘッド速度３００ｍｍ／分で測定する。
【００５２】
【実施例１】
常法により調製したエチレンと一酸化炭素が完全交互共重合した、極限粘度６．０のポリケトンを、塩化カルシウム３０質量％／塩化亜鉛２２質量％／塩化リチウム１０質量％を含有する水溶液に溶解して、ポリケトン濃度６．５質量％のドープを得た。得られたドープを８０℃に加温し、紡口径０．１５ｍｍφ、ホール数２５０の紡口より１０ｍｍのエアーギャップを通した後に、２質量％の塩化カルシウム、１．１質量％の塩化亜鉛及び０．１質量％の塩酸を含有する−２℃の水からなる凝固浴中に押し出した。
【００５３】
引き続き、糸条を塩酸水溶液、水で順次洗浄した後に、ＩＲＧＡＮＯＸ（登録商標）１０９８（Ｃｉｂａ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ社製）、ＩＲＧＡＮＯＸ（登録商標）１０７６（Ｃｉｂａ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ社製）をそれぞれ０．０５質量％づつ（対ポリケトン）配合した後に、２２５℃にて定長乾燥した。
乾燥した繊維に、セチルホスフェートカリウム塩（モノセチルホスフェートカリウム塩／ジセチルホスフェートカリウム塩＝６０質量％／４０質量％）の１０質量％水分散液を浸漬法により付与し、引き続き、２２５℃／２４０℃／２５０℃／２５７℃でそれぞれ６．５倍／１．５倍／１．３倍／１．２倍の、トータル１５．２倍の４段延伸を行い、総繊度２５２ｄｔｅｘのポリケトン繊維を得た。
【００５４】
延伸性は極めて良好で、延伸時に単糸巻き付きや断糸等のトラブルは発生しなかった。得られたポリケトン繊維は、高強度で、毛羽やフィブリル状物は観察されず、集束性に優れた極めて高性能、かつ、高品位のものであった。
本発明の実施例１〜８及び比較例１〜７で作製したポリケトン繊維の構造及び特性を、それぞれ表１及び２にまとめて示す。また、実施例９〜１１の撚糸コード、紡績糸に用いた４段延伸終了後のポリケトン繊維の構造及び特性も表１に併せて示す。
【００５５】
【実施例２】
実施例１において、乾燥後のポリケトン繊維に付与するイオン性化合物を、ステアリルホスフェートカリウム塩（モノステアリルホスフェートカリウム塩／ジステアリルホスフェートカリウム塩＝５０質量％／５０質量％）の１０質量％水分散液とする以外は同様にして紡糸、延伸を行った。延伸性は良好で、得られたポリケトン繊維も高性能、かつ、高品位であった。
【００５６】
【実施例３】
実施例１において、乾燥後のポリケトン繊維に付与するイオン性化合物を、オクチルホスフェートカリウム塩（モノオクチルホスフェートカリウム塩／ジオクチルホスフェートカリウム塩＝４５質量％／５５質量％）の１０質量％水分散液とする以外は同様にして紡糸、延伸を行った。延伸性は良好で得られたポリケトン繊維も高性能、高品位であった。
【００５７】
【実施例４】
実施例１において、乾燥後のポリケトン繊維に付与するイオン性化合物を、アルキルスルホネートナトリウム塩（アルキルはＣ１０〜Ｃ１５の直鎖飽和炭化水素の混合物）の１０質量％水分散液とする以外は同様にして紡糸、延伸を行った。延伸性は良好で得られたポリケトン繊維も高性能、かつ、高品位であった。
【００５８】
【実施例５】
実施例１において、乾燥後のポリケトン繊維に付与するイオン性化合物を、ジポリオキシエチレンラウリルエーテルホスフェートカリウム塩（エチレンオキサイド２モル付加物）の１０質量％水分散液とする以外は同様にして紡糸、延伸を行った。延伸性は良好で得られたポリケトン繊維も高性能、かつ、高品位であった。
【００５９】
【実施例６】
実施例１において、乾燥後のポリケトン繊維に付与するイオン性化合物を、モノイソセチルホスフェートカリウム塩／モノラウリン酸ナトリウム（＝６０質量％／４０質量％）混合物の１０質量％水分散液とする以外は同様にして紡糸、延伸を行った。延伸性は良好で得られたポリケトン繊維も高性能、高品位であった。
【００６０】
【実施例７】
実施例１において、イオン性化合物の濃度を２０質量％の水分散液として、乾燥後及び１段延伸後の２段階で付与する以外は同様にして紡糸、延伸を行った。延伸性は良好で得られたポリケトン繊維も高性能、かつ、高品位であった。
【００６１】
【実施例８】
実施例１において、イオン性化合物の濃度を２質量％の水分散液とする以外は同様にして紡糸、延伸を行った。延伸性は良好で得られたポリケトン繊維も高性能、かつ、高品位であった。
【００６２】
【実施例９】
実施例１において、得られた乾燥糸６本を合糸する以外は同様にしてイオン性化合物を付与、４段延伸を行い、繊度１６５５ｄｔｅｘ／１５００ｆのマルチフィラメントを得た。工程通過性は極めて良好で、延伸時に毛羽や断糸は全く発生せず、強度も優れていた。
得られたポリケトン繊維をＺ方向に３９０回／ｍで下撚り（下撚り張力０．０５ｃＮ／ｄｔｅｘ）し、これを２本双糸し、Ｓ方向に３９０回／ｍ上撚り（上撚り張力０．０５ｃＮ／ｄｔｅｘ）してコードを製造した。撚糸時の工程通過性は良好であり、毛羽やガイド上への糸の巻き付きは発生せず、得られたコードも毛羽やフィブリル状物のほとんどない品位の優れたものであった。撚糸物の強度は１３．３ｃＮ／ｄｔｅｘと高く、撚糸協力利用率（撚糸後のコードの協力を撚糸前の繊維の強力で除した１００分率）は７５．１％と非常に優れたものであった。
【００６３】
【実施例１０】
実施例９において、４段延伸終了時にポリケトン繊維にローラー法で仕上げ剤を付与して巻き取る以外は同様にして紡糸、合糸、延伸、撚糸を行った。仕上げ剤は下記の組成のものを用いた。
オレイン酸ラウリルエステル／ビスオキシエチルビスフェノールＡ／ポリエーテル（プロピレンオキシド／エチレンオキシド＝３５／６５：分子量２００００）／ポリエチレンオキシド１０モル付加オレイルエーテル／ポリエチレンオキシド１０モル付加ひまし油エーテル／ステアリルスルホン酸ナトリウム／ジオクチルリン酸ナトリウム＝３０／３０／１０／５／２３／１／１（質量％比）。
【００６４】
仕上げ剤の付着率は１．８質量％（対ポリケトン繊維）であった。撚糸性は良好で、撚糸時に毛羽や単糸の巻き付き等のトラブルは発生しなかった。
得られたコードを、下記の液組成のＲＦＬ（レゾルシン−ホルマリン−ラテックス）液に浸漬した後に、乾燥ゾーン（張力３Ｎで１６０℃で１２０秒の熱処理）、ヒートセットゾーン（張力４．２Ｎで２２０℃で６０秒の熱処理）、ノルマライジングゾーン（張力２．８Ｎで２２０℃、６０秒の熱処理）を通してＲＦＬ処理コードを得た。
（ＲＦＬ液組成）
レゾルシン ２２．０部
ホルマリン（３０質量％） ３０．０部
水酸化ナトリウム（１０質量％） １４．０部
水 ５７０．０部
ビニルピリジンラテックス（４１質量％） ３６４．０部
得られたＲＦＬ樹脂付着ポリケトンコードは撚糸強力利用率が７３．５％と高く、ゴムとの接着力も１６５Ｎ／ｃｍ／ｃｏｒｄと非常に高いものであった。
【００６５】
【実施例１１】
実施例１において、乾燥糸１２本を合糸した後にイオン性化合物を付与する以外は同様にして紡糸、延伸を行い総繊度３１５０ｄｅｔｘのポリケトン繊維を得た。得られたポリケトン繊維を押し込み型捲縮機で捲縮を付与し、次いで２２０℃で熱固定を行い、引き続きロータリーカッターにて短繊維に切断し、単糸繊度０．９ｄｔｅｘ、平均繊維長７１ｍｍのポリケトン短繊維を得た。
このポリケトン短繊維をスライバ状にして、７５０Ｔ／ｍの片撚り（Ｚ撚り）を加えて、繊度１２０ｄｔｅｘの紡績糸を製造した。紡績時の工程通過性は良好で、カードへの糸屑や油の付着による汚れや単糸の絡みつき等の問題はなく、また、得られた紡績糸は、引っ張り強度が７．５ｃＮ／ｄｔｅｘと高強度のものであった。
【００６６】
【比較例１】
実施例１において、イオン性化合物を付与しない以外は同様にして延伸を行った。１段延伸直後からロール上やガイド上で静電気による糸束の拡がりが観察され、３段延伸のフィードロール上では隣接するフィラメントの単糸どうしが重なり合い、単糸切れが発生した。得られた繊維は、強度は高いものの、静電気による反発によって糸の解舒性が悪く、毛羽やフィブリル状物の多い品位の劣るものであった。
【００６７】
【比較例２】
実施例１において、イオン性化合物の代わりに鉱物油（レッドウッド粘度１００秒のパラフィンワックス）を付与した。１段延伸時及び２段延伸時に糸束からの発煙が観察された。延伸性は不良で、静電気による糸束の拡がり、ロール上での単糸重なりによる単糸切れが発生した。得られた繊維は強度は高かったものの、毛羽が多く品位の劣るものであった。
【００６８】
【比較例３】
実施例１において、イオン性化合物の代わりにポリオキシエチレンラウリルエーテル（ＥＯ２０モル付加物）を付与した。延伸性は不良で、多段延伸の２段目で断糸が起こり高倍率の延伸を行うことができなかった。
【００６９】
【比較例４】
実施例１において、イオン性化合物の代わりにソルビタンモノステアレート／ポリオキシエチレンステアリルエーテル（ＥＯ２０モル付加物）／ポリオキシエチレンオレイルエーテル（ＥＯ３モル付加物）＝（３７．５／２５／３７．５質量％）を付与した。延伸性は不良で、多段延伸の３段目で断糸が起こり高倍率の延伸を行うことができなかった。
【００７０】
【比較例５】
実施例１において、イオン性化合物の代わりに下記の組成の油剤を付与した
オレイン酸ラウリルエステル／ビスオキシエチルビスフェノールＡ／ポリエーテル（プロピレンオキシド／エチレンオキシド＝３５／６５：分子量２００００）／ポリエチレンオキシド１０モル付加オレイルエーテル／ポリエチレンオキシド１０モル付加ひまし油エーテル／ステアリルスルホン酸ナトリウム／ジオクチルリン酸ナトリウム＝３０／３０／１０／５／２３／１／１（質量％比）。
延伸時に断糸はなかったものの、ガイドへの単糸巻き付きが発生した。また、４段延伸後の繊維は茶褐色に着色し、単糸どうしが膠着していた。得られた繊維の強度は実施例１に比べて１０％以上も低下していた。
【００７１】
【比較例６】
実施例１において、イオン性化合物の代わりにオレイルアミン酢酸塩を付与した。延伸性は不良で、多段延伸の２段目で断糸が起こり高倍率の延伸を行うことができなかった。
【００７２】
【比較例７】
実施例１において、付与するイオン性化合物を濃度４０質量％の水分散液として、２段階で付与する以外は同様にして紡糸、延伸を行った。得られた延伸糸は茶色に着色し、ガイド及びロール上に白色状物の析出が観察された。
【００７３】
【表１】

【００７４】
【表２】

【００７５】
【発明の効果】
本発明のポリケトン繊維は、制電性、集束性、耐摩耗性に優れる。また、製造に際して、延伸時の工程通過性、さらには、強度、品位、取り扱い性、後加工における工程通過性に優れる。
本発明のポリケトン繊維は、フィラメント数の多い産業資材用途であっても優れた性能、品位を有し、タイヤコード、ロープ、ベルト、耐震補強材、セメント補強材、樹脂補強材等の複合材料や紡績糸等の衣料材料に特に有用である。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a polyketone fiber excellent in antistatic property and bundling property, and further excellent in quality, process passability and processability, a spun yarn and a twisted yarn cord containing the polyketone fiber, and a production method thereof.
[0002]
[Prior art]
In recent years, it is known that a polyketone in which carbon monoxide and an olefin are completely alternately copolymerized can be obtained by polymerizing carbon monoxide and an olefin such as ethylene or propylene using palladium or the like as a catalyst.
Fiber made of polyketone has high strength, high elastic modulus, high heat resistance, high adhesion and high creep resistance, and is used for reinforcing products such as rubber products such as tires, belts and hoses, cement, resins, optical fibers, Expected to be used in a wide range of fields such as ropes, fishing nets, fishing line and other leisure and fishery applications, civil engineering nets, waterproof fabrics, insulation fabrics and other civil engineering and construction materials, protective clothing, cut-resistant gloves and other clothing applications Yes.
[0003]
Regarding polyketone fibers having high strength and high elastic modulus and methods for producing the same, there have been many documents (for example, JP-A-4-228613, JP-A-4-505344, JP-A-7-508317). No. 8/507328, WO 99/18143 pamphlet, WO 00/09611 pamphlet, etc.), high melting point polyketone fiber having 1-oxotrimethylene as a main repeating unit is polyketone. It is known that it is produced by a wet spinning method in which it is dissolved in an organic solvent or an inorganic solvent to form a fiber.
[0004]
According to these documents, in order to produce a polyketone fiber having high strength and high elastic modulus, it is necessary to heat the polyketone fiber obtained by wet spinning at a high temperature near the melting point and perform high-strength heat drawing. Is disclosed.
The polyketone fiber produced by high-strength hot drawing is charged with static electricity due to the friction between the fiber and the fiber and between the fiber and the production apparatus at the time of drawing, and the convergence of the yarn is lowered. This tendency becomes more prominent as the number of single yarns of the polyketone fiber used for drawing increases and as the drawing speed increases. When the antistatic and converging properties of the yarn at the time of hot drawing are poor, not only the quality of the resulting fiber and the package foam are deteriorated, but also the contact resistance between the fibers and between the fibers and the device is increased. From the viewpoint of productivity, yarn breakage and fibrillation of the fiber surface occur, and single yarns and fluff are wound around rolls and guides.
[0005]
In industrial material fiber applications, fibers with high strength and a large number of filaments are required. However, in the case of polyketone fibers, it is extremely difficult to draw multifilament fibers at high speed due to the above-mentioned problems of antistatic properties and bundling properties. It was difficult.
Generally, in order to suppress the static electricity of the fiber and improve the convergence, it is effective to apply an oil agent to the fiber. The inventors of the present invention have proposed a technique relating to polyketone fibers provided with an oil agent in Japanese Patent Application Laid-Open No. 2001-207384 regarding a technique for applying an oil agent to a polyketone fiber. However, the oil agent used in the present invention is mainly composed of a smoothing agent such as mineral oil, polyether, ester compound, etc., and although the anti-friction property of the fiber is improved, the antistatic property at the time of stretching is described above. There was still room for improvement in terms of convergence.
[0006]
For example, oils based on mineral oil have room for improvement in antistatic properties and sizing properties, and oils based on polyethers and ester compounds have improved antistatic properties and sizing properties depending on the composition. However, the oil agent is likely to deteriorate due to heat during the production of the fiber. When short fibers of polyketone fibers are used as spun yarn, the oil agent mainly composed of polyether or ester compound needs to be provided with a large amount of oil agent in order to impart antistatic properties to the polyketone fiber. Oil easily accumulates in cards and checkers in the process.
[0007]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to solve the problems of antistatic property, bundling property, and process passability of the polyketone fiber,
(1) By applying a stretched oil agent, static electricity is not generated, fiber convergence is increased, fiber frictional resistance is reduced, and there is no fuzz or sagging, it is easy to handle, high strength, twisted yarn Providing polyketone fibers with excellent utilization and spinnability,
(2) To provide a production method capable of stretching a polyketone fiber composed of a large number of filaments at high speed with high productivity,
It is.
[0008]
[Means for Solving the Problems]
As a result of various studies to solve the above-mentioned problems, the present inventors have added a compound having a specific structure as an oil agent to reduce antistatic property, convergence property and frictional resistance to the polyketone fiber. It was found that the problems of process deterioration due to deterioration of oil, deterioration of polyketone fiber strength and strength utilization rate, and decrease in process passability during spinning were found to be effective. As a result, the present invention has been completed.
[0009]
  That is, the present invention is as follows.
(1) A polyketone fiber in which 95 to 100% by mass of the repeating unit is 1-oxotrimethylene, and at least one ionic compound selected from the group consisting of the following (a) to (d) is a polyketone 0.05 to fiber1% by massAdhereAnd the adhesion amount of oil agent components other than the following (a)-(d) is 0-30 mass% with respect to the total adhesion amount of the ionic compound of (a)-(d).Polyketone fiber characterized by that.
  (A) R¹-P (= O) (OX¹) (OX²)
  (B) R²-P (= O) (OR^Three) (OX^Three)
  (C) R^Four-S (= O) (OX^Four)
  (D) R^Five-C (= O) (OX^Five)
(Where X¹~ X^FiveIs hydrogen, alkali metal, alkaline earth metal, and NH_FourAt least one selected from the group consisting of R¹~ R^FiveIs an organic group having 3 to 30 carbon atoms)
[0010]
(2) 95 to 100% by mass of the repeating unit is made of polyketone having 1-oxotrimethylene, the average fiber length is 10 to 200 mm, and the polyketone fiber having a crimp degree of 5 to 50% is 50% by mass or more. A spun yarn containing at least one ionic compound selected from the group consisting of the following (a) to (d) is attached to 0.05 to 1% by mass with respect to the spun yarn.And the adhesion amount of oil agent components other than the following (a)-(d) is 0-30 mass% with respect to the total adhesion amount of the ionic compound of (a)-(d).A spun yarn characterized by this.
  (A) R¹-P (= O) (OX¹) (OX²)
  (B) R²-P (= O) (OR^Three) (OX^Three)
  (C) R^Four-S (= O) (OX^Four)
  (D) R^Five-C (= O) (OX^Five)
(Where X¹~ X^FiveIs hydrogen, alkali metal, alkaline earth metal, and NH_FourAt least one selected from the group consisting of R¹~ R^FiveIs an organic group having 3 to 30 carbon atoms)
[0011]
(3) A twisted cord comprising a polyketone fiber in which 95 to 100% by mass of the repeating unit is 1-oxotrimethylene, and twisted in a range of a twist coefficient (K) represented by the following formula of 1000 to 30000. Then, at least one ionic compound selected from the group consisting of the following (a) to (d) is 0.05 to1% by massAdhereAnd the adhesion amount of oil agent components other than the following (a)-(d) is 0-30 mass% with respect to the total adhesion amount of the ionic compound of (a)-(d).A twisted yarn cord characterized by that.
                K = Y × D^0.5
  (Where Y is the number of twists per meter (T / m), and D is the total fineness (dtex) of the polyketone fibers used in the twisted yarn)
  (A) R¹-P (= O) (OX¹) (OX²)
  (B) R²-P (= O) (OR^Three) (OX^Three)
  (C) R^Four-S (= O) (OX^Four)
  (D) R^Five-C (= O) (OX^Five)
(Where X¹~ X^FiveIs hydrogen, alkali metal, alkaline earth metal, and NH_FourAt least one selected from the group consisting of R¹~ R^FiveIs an organic group having 3 to 30 carbon atoms)
[0012]
(4) In a method for producing a polyketone fiber, comprising a step of spinning a polyketone comprising 95 to 100% by mass of repeating units consisting of 1-oxotrimethylene and a step of drawing the spun polyketone fiber by applying heat; And / or at least one ionic compound selected from the group consisting of the following (a) to (d) in the course of stretching: 0.05 to1% by massThe manufacturing method of the polyketone fiber characterized by including the process to provide.
  (A) R¹-P (= O) (OX¹) (OX²)
  (B) R²-P (= O) (OR^Three) (OX^Three)
  (C) R^Four-S (= O) (OX^Four)
  (D) R^Five-C (= O) (OX^Five)
(Where X¹~ X^FiveIs hydrogen, alkali metal, alkaline earth metal, and NH_FourAt least one selected from the group consisting of R¹~ R^FiveIs an organic group having 3 to 30 carbon atoms)
[0013]
(5) 95 to 100% by mass of the repeating unit is 1-oxotrimethylene, and at least one ionic compound selected from the group consisting of the following (a) to (d) is 0. Manufacture of spun yarn, characterized in that the polyketone fiber adhering to 05 to 1% by mass is cut into an average fiber length of 5 to 300 mm to produce a sliver with a polyketone fiber ratio of 50 to 100% by mass, followed by spinning. Method.
(A) R¹-P (= O) (OX¹(OX²)
(B) R²-P (= O) (OR^Three) (OX^Three)
(C) R^Four-S (= O) (OX^Four)
(D) R^Five-C (= O) (OX^Five)
(Where X¹~ X^FiveIs hydrogen, alkali metal, alkaline earth metal, and NH_FourAt least one selected from the group consisting of R¹~ R^FiveIs an organic group having 3 to 30 carbon atoms)
The polyketone used in the present invention contains 1-oxotrimethylene in which 95 to 100% by mass of the repeating unit is represented by the formula (1).
[0014]
[Chemical 1]

[0015]
When the proportion of 1-oxotrimethylene in the polyketone is less than 95% by mass, the crystallinity is greatly lowered, and a polyketone fiber having high strength and a high melting point cannot be obtained. The higher the proportion of 1-oxotrimethylene, the higher the strength, elastic modulus and melting point of the polyketone fiber. A preferred ratio of 1-oxotrimethylene in the polyketone is 97% by mass or more, more preferably 100% by mass.
As the intrinsic viscosity of the polyketone becomes lower, it becomes difficult to obtain high-strength physical properties, and as it becomes higher, the solubility in a solvent, the spinnability and the productivity are lowered. Therefore, the intrinsic viscosity of the polyketone is preferably 1 to 20, more preferably 3-10, most preferably 4-8.
[0016]
At least one ionic compound selected from the group consisting of the following (a) to (d) is adhered to the polyketone fiber of the present invention in an amount of 0.05 to 5% by mass with respect to the polyketone fiber. Is extremely important.
(A) R¹-P (= O) (OX¹) (OX²)
(B) R²-P (= O) (OR^Three) (OX^Three)
(C) R^Four-S (= O) (OX^Four)
(D) R^Five-C (= O) (OX^Five)
Where X¹~ X^FiveIs hydrogen, alkali metal, alkaline earth metal, and NH_FourAt least one selected from the group consisting of R¹~ R^FiveIs an organic group having 3 to 30 carbon atoms.
[0017]
The compound adhering to the polyketone fiber of the present invention is an ionic compound (phosphoric acid compound, phosphorous acid compound, sulfonic acid compound, carboxylic acid compound). Nonionic compounds that do not have ionic functional groups and have only nonionic groups such as ethers, esters, and ketones do not exhibit sufficient antistatic properties, but also have dirt and strength due to thermal degradation during hot stretching. Causes a drop.
A group (X that binds to a functional group (phosphoric acid group, phosphorous acid group, sulfonic acid group, carboxylic acid group) of an ionic compound)¹~ X^Five) Is hydrogen, alkali metal, alkaline earth metal, and NH_FourIt is necessary to be at least one selected from the group consisting of When this bonding group is a hydrocarbon group or the like, it becomes difficult to produce a polyketone fiber excellent in antistatic property and focusing property. This bonding group is preferably an alkali metal, more preferably potassium or sodium, from the viewpoint of antistatic properties, bundling properties and fiber properties of the polyketone fiber. This linking group may exist as a mixture of a plurality of groups.
[0018]
The ionic compound in the present invention is an organic group having 3 to 30 carbon atoms, preferably 4 to 18 carbon atoms (R¹~ R^Five). When there is no organic group, or when the organic group has 2 or less carbon atoms, the affinity of the ionic compound with respect to the polyketone fiber is low, and it is difficult to disperse uniformly on the fiber surface. The oil film strength of the polyketone fiber decreases, the wear resistance and impact resistance of the polyketone fiber decrease, the single yarn breaks and the fibrillation of the fiber surface occurs during stretching, twisting, spinning and the like. When the number of carbon atoms exceeds 30, the antistatic property becomes insufficient, the converging property of the filament decreases, the frictional resistance increases, and the fluff and fibrillation easily occur during stretching and twisting. There arises a problem that the unwinding property and the winding form of the package are not uniform.
[0019]
The structure of the organic group is not limited, and may be, for example, a saturated aliphatic group, an unsaturated aliphatic group, an aromatic group, or a hydrocarbon group in which these are mixed. It may be substituted with a group such as an ether group, ester group, ketone group, hydroxyl group, amide group, sulfonic acid group, phosphoric acid group or carboxylic acid group. From the viewpoint of the heat resistance of the ionic compound, a saturated aliphatic hydrocarbon group is preferred. The organic group may be linear or branched. Further, the organic group may be a mixture of a plurality of types having different structures, and is preferably a mixture from the viewpoint that crystals of an ionic compound are difficult to precipitate on the apparatus.
[0020]
Examples of the ionic compound having the above characteristics include the following compounds, but are not limited thereto.
Examples of compounds (a) and (b) include alkyl phosphate esters (octyl phosphate potassium salt, cetyl phosphate potassium salt, stearyl phosphate potassium salt, lauryl phosphate potassium salt, palmityl phosphate potassium salt, isopropyl phosphate potassium salt, Cetyl phosphate potassium salt, cetyl phosphate sodium salt, cetyl phosphate ammonium salt, etc.), alkyl ether phosphate (polyoxyethylene cetyl ether phosphate potassium salt, polyoxyethylene lauryl ether phosphate sodium salt, polyoxyethylene stearyl ether phosphate ammonium salt, etc.), Alkyl allyl ether phosphate (nonyl phenyl ether phosphate potassium salt, etc.) It is.
[0021]
Examples of the compound (c) include alkyl allyl sulfonate (such as dodecylbenzene sulfonate sodium salt), alkyl sulfonate (such as octyl sulfonate potassium salt), alkyl naphthalene sulfonate (dibutyl naphthalene sulfonate sodium salt, triisopropyl naphthalene sulfonate sodium salt, etc.), Alkyl sulfosuccinate (dioctyl sulfosuccinate sodium salt, etc.), alkyl sulfate (octyl sulfate sodium salt, etc.), alkyl ether sulfate (lauryl ether sulfate sodium salt, etc.), alkyl allyl ether sulfate (nonyl phenyl ether sulfate sodium salt, etc.), etc. Is mentioned.
[0022]
Examples of the compound (d) include fatty acid soap (sodium stearate), polycarboxylic acid soap (castor oil sodium soap, etc.) and the like.
The compounds (a) to (d) may be used by mixing them.
In the present invention, it is important that the ionic compound adheres to the polyketone fiber in an amount of 0.05 to 5% by mass, preferably 0.1 to 1% by mass. If the adhesion rate is less than 0.05% by mass, the antistatic property and the focusing property are insufficient, and there is a problem in the quality and process passability. On the other hand, when the amount exceeds 5% by mass, the oil agent adheres to the apparatus during stretching or processing and the apparatus becomes very dirty, and in some cases, crystals precipitate and cause yarn breakage.
[0023]
In addition to the above ionic compound, the polyketone fiber of the present invention may contain additives such as radical inhibitors, other polymers, matting agents, ultraviolet absorbers, flame retardants and the like as necessary. .
The polyketone fiber of the present invention has an oil component other than the above ionic compounds, an antiseptic, and an antioxidant as long as the antistatic property, bundling property, fiber physical properties are not impaired, and the process passability is not adversely affected. An agent, an emulsifier, a rust inhibitor and the like may be added. There is no restriction | limiting in the oil agent component which can be used, It is possible to select suitably according to the objectives, such as an improvement in smoothness, a convergence supplement, and antistatic supplement.
[0024]
Examples of such compounds include ester compounds such as octyl stearate and lauryl oleate, paraffinic and naphthenic mineral oils, polyethers such as polyolefin oxide, nonionic surfactants such as polyoxyethylene stearyl ether, Examples include cationic compounds such as stearylamine methyl sulfonate and octylamine dimethyl phosphate. If the amount of these oil agent components is too large, the antistatic property is impaired, or the cause of problems such as fiber physical property deterioration due to thermal deterioration of the oil agent at the time of hot drawing, deterioration of process passability, reduction of twisted yarn strength utilization rate, etc. Therefore, it is preferably 0 to 100% by mass, preferably 0 to 50% by mass, and most preferably 0 to 30% by mass with respect to the total adhesion amount of the ionic compounds (a) to (d). .
[0025]
The polyketone fiber of the present invention is required to have excellent mechanical properties and thermal properties in order to be used for general purposes, and for that purpose, it is required to have a developed crystal structure. Specifically, the polyketone fiber of the present invention preferably has a crystallinity of 60% or more and a crystal orientation of 90% or more. The higher the degree of crystallinity, the higher the strength, elastic modulus, and melting point. Therefore, it is more preferably 70% or more, and most preferably 80% or more. The higher the degree of crystal orientation, the higher the elastic modulus and the better the mechanical dimensional stability. Therefore, it is more preferably 95% or more, and most preferably 97% or more.
[0026]
The polyketone fiber of the present invention desirably has excellent strength and elastic modulus as mechanical properties, and the strength is preferably 12 cN / dtex or more, more preferably 15 cN / dtex or more, and most preferably 17 cN / dtex or more. . The elastic modulus is preferably 250 cN / dtex or more, more preferably 300 cN / dtex or more, and most preferably 350 cN / dtex or more.
The cross-sectional shape of the polyketone fiber of the present invention may be any shape, and an arbitrary shape such as a circular shape, a triangular shape, or an alphabetic character shape can be selected according to the purpose. A circular cross-section is preferable from the viewpoints that friction is small, fibrillation is difficult, and single yarn sticking hardly occurs.
[0027]
There is no restriction | limiting in the form of a polyketone fiber, Any of a long fiber and a short fiber may be sufficient. In the case of a long fiber, either a monofilament or a multifilament may be used. The number of filaments in the case of a multifilament is preferably 100 or more, more preferably 200 or more, and most preferably 300 or more.
There is no restriction on the single yarn fineness of the polyketone fiber of the present invention, but if it is too thin, yarn is likely to break during spinning, stretching, processing, use, etc.If it is too thick, it is difficult to increase the spinning speed. Therefore, it is preferably 0.1 to 10 dtex, more preferably 0.5 to 5 dtex, and most preferably 0.8 to 2 dtex.
[0028]
The total fineness may be appropriately selected according to the application and purpose. For example, it is preferably 300 to 7000 dtex for industrial materials and 50 to 1000 dtex for clothing. The polyketone fiber of the present invention is excellent in antistatic property and bundling property, and particularly excellent in process passage property, handling property and post-processing property in multifilament, and can be formed into a very large number of fibers. In particular, it is easy to handle as tow and is very suitable for the production of short fibers. Tow is a fiber bundle in which the filaments are aligned and the total fineness is 1000 dtex or more. In the case of a tow used for the production of short fibers, the total fineness is preferably 1000 to 1000000 dtex, and more preferably 3000 to 300000 dtex from the viewpoint of productivity and handleability.
[0029]
The polyketone fiber of the present invention can be easily produced and processed as a tow having a large fineness, and is suitable for use as a short fiber by cutting the tow. In the case of short fibers, the average fiber length is preferably 5 to 300 mm from the viewpoints of process passability and handleability.
One of the preferred uses when the polyketone fiber of the present invention is used as a short fiber is spun yarn. Processing into a spun yarn involves a process of applying friction or drawing to the fiber, such as a card or check roll, which causes generation of fuzz and fibrils due to the friction and wear of the fiber, and equipment contamination due to excess oil. Happens. However, the polyketone fiber of the present invention improves the antistatic property and wear resistance by adhering a very small amount of the ionic compound to the fiber, so that the spun yarn does not cause such problems. Can be processed.
[0030]
In the case of producing a spun yarn, the ratio of the ionic compounds (a) to (d) given to the spun yarn needs to be 0.05 to 1% by mass, preferably 0.1 to 0.1% by mass. 0.3% by mass. When the applied ratio is less than 0.05% by mass, the antistatic property and wear resistance are insufficient, and problems such as entanglement of fibers due to static electricity and generation of fibrils occur in the card. On the other hand, if it exceeds 1% by mass, excessive oil agent adheres to the card or check roll, the device becomes dirty, and long-term continuous operation becomes difficult.
[0031]
The average fiber length of the polyketone fiber constituting the spun yarn is 10 to 200 mm, preferably 20 to 150 mm, more preferably 30 to 100 mm. When the average fiber length is less than 10 mm, entanglement and friction between short fibers are reduced, and it becomes difficult to obtain a high-strength spun yarn. On the other hand, when the average fiber length exceeds 200 mm, not only does the process passability during spinning, weaving, knitting, etc. worsen, but it becomes difficult to obtain spun yarns and knitted fabrics with good texture and quality.
[0032]
The degree of crimp of the polyketone fiber constituting the spun yarn needs to be 5 to 50%, preferably 10 to 30%. When the degree of crimp is small, the entanglement and friction between the polyketone fibers are reduced, and the fibers are easily pulled out. As a result, it becomes difficult to obtain a high-strength spun yarn. On the other hand, if the degree of crimp is too large, sagging and entanglement of the fibers occur, the process passability during spinning, weaving and knitting deteriorates, and the quality of the spun yarn and woven or knitted fabric obtained is low.
[0033]
The polyketone spun yarn preferably has a twist coefficient (K) represented by the following formula of 3000 to 30000, and more preferably 7500 to 15000.
K = Y × D^0.5(T / m · dtex^0.5)
In the formula, Y is the number of twisted yarns per meter (T / m), and D is the fineness (dtex) of the spun yarn.
When the twist coefficient (K) is too low, the frictional resistance between the short fibers in the tensile direction becomes insufficient, and the strength and elongation of the spun yarn become insufficient. On the other hand, if the twist coefficient (K) is too high, the twist strength utilization rate of the polyketone fiber is greatly reduced, and it becomes difficult to obtain a spun yarn having sufficient strength.
[0034]
The spun yarn comprising the polyketone fiber of the present invention is 50% by mass or more of the fiber constituting the spun yarn, and from the viewpoint of the strength and cost of the spun yarn, preferably 70% by mass or more is a polyketone fiber. A blended yarn using fibers may be used. The average fiber length, the degree of crimp, and the amount of ionic compound attached to the fibers to be mixed need to be within the range of values necessary for the polyketone fiber used for the spinning. Fibers that can be blended with polyketone fibers are not limited. Synthetic fibers such as viscose rayon, polyethylene terephthalate fibers, polytrimethylene terephthalate fibers, nylon 66 fibers, nylon 6 fibers, acrylic fibers, aramid fibers, polyvinyl alcohol fibers, cotton Natural fibers such as wool, hemp and silk can be used.
[0035]
The polyketone fiber of the present invention can be used as a twisted cord by twisting the filament as it is. In this case, the adhesion rate of the ionic compound to the twisted cord needs to be 0.05 to 5% by mass, and preferably 0.1 to 1% by mass. When the adhesion rate of the ionic compound is less than 0.05% by mass, the antistatic property of the fibers constituting the twisted yarn cord is insufficient, and the single yarn frays or sags. On the other hand, when it exceeds 5% by mass, an excessive ionic compound is deposited on the guide or the roll, and the yarn is liable to be soiled or broken.
[0036]
The twist coefficient (K) represented by the following formula when twisting is 1000 to 30000, preferably 5500 to 15000.
K = Y × D^0.5(T / m · dtex^0.5)
In the formula, Y is the number of twists per meter (T / m), and D is the total fineness (dtex) of the polyketone fiber used for the twisted yarn.
When the twist coefficient (K) is less than 1000, the elongation and toughness of the twisted cord are insufficient, and the fatigue resistance against bending and compression becomes insufficient. On the other hand, when the twist coefficient (K) exceeds 30000, the twisted yarn strength utilization rate is significantly lowered, and it becomes difficult to obtain a twisted yarn cord having sufficient strength.
A treated cord obtained by adhering a resin such as resorcin-formalin-latex (RFL) to this twisted cord has high adhesiveness to rubber and is useful as a rubber reinforcing material for tires, belts, hoses and the like.
[0037]
Next, the manufacturing method of the polyketone fiber of this invention is demonstrated.
The polyketone fiber of the present invention is preferably produced by making it into a fibrous form by a known wet spinning method (the polyketone is dissolved in a solvent and then coagulating in a coagulation bath), and removing the solvent and drying to perform hot drawing. It is done. In order to industrially produce high-strength polyketone fibers with high productivity, a wet spinning method using a metal salt solution as a solvent is more preferable.
[0038]
Hereinafter, a wet spinning method using a metal salt solution as a solvent will be described as an example.
Solutions containing polyketone containing zinc halide, alkali metal halide, alkaline earth metal halide, alkali metal thiocyanate, alkaline earth metal thiocyanate, etc. (for example, zinc chloride / calcium chloride aqueous solution, zinc chloride / calcium chloride / Dissolved in calcium thiocyanate aqueous solution). The dissolved solution is discharged from a spinneret into a liquid such as water to form a thread, and then the metal salt is washed away with an acid aqueous solution such as hydrochloric acid. Next, drying is performed at 100 to 250 ° C., and a liquid such as water remaining in the fiber is removed to 10% by mass or less, preferably 1% by mass or less with respect to the polyketone fiber.
[0039]
In the drying, the drying ratio represented by the ratio (yarn length after drying / yarn length before drying) is preferably 0.7 to 3 times, and more preferably 0.8 to 1.5 times.
The dried yarn (hereinafter referred to as dry yarn) is subsequently stretched by applying heat. The higher the heat draw ratio is, the higher the polyketone fiber having higher strength and higher elastic modulus is obtained. Therefore, it is preferably 5 times or more, more preferably 10 times or more, and most preferably 15 times or more. The number of stretching stages may be one, but when stretching at a high magnification of 10 times or more, multi-stage stretching of 2 or more stages is preferable. The stretching temperature is preferably 150 to 280 ° C, more preferably 220 to 275 ° C. When performing multi-stage stretching, it is preferable to perform temperature-raising thermal stretching in which the stretching temperature is gradually increased as the number of stretching stages proceeds. If necessary, it is preferable to heat the polyketone fiber after heat drawing to 100 to 280 ° C. and heat-treat with a tension of 0.001 to 1 cN / dtex to suppress thermal shrinkage of the polyketone fiber.
[0040]
The ionic compounds of the above (a) to (d) are preferably applied at any stage of drying, hot stretching and heat treatment processes, and in particular, the ionic compound is applied at any stage before hot stretching. It is preferable to improve the antistatic property and sizing property of the polyketone fiber during hot drawing.
The application of the ionic compound may be performed in multiple stages. For example, in the multistage stretching, the ionic compound may be applied first before the thermal stretching and then in two stages during the thermal stretching. The adhesion rate of the ionic compound to the polyketone fiber needs to be 0.05 to 5% by mass, and preferably 0.1 to 1% by mass. When the adhesion rate is less than 0.05% by mass, the antistatic property and the focusing property at the time of stretching are insufficient, and fluffing and fibrillation are liable to occur, which adversely affects process passability and product quality. On the other hand, when the adhesion rate exceeds 5% by mass, the apparatus becomes dirty, especially the guides and rolls become so dirty that long-term continuous operation becomes difficult.
[0041]
The ionic compound may be applied in any form, and can be used in any form such as straight, aqueous solution, aqueous dispersion and the like. As a method for applying the ionic compound, a known method such as a spray method, a roller oil supply method, a guide oil supply method using a metering pump, or the like can be used as it is.
A finishing agent is imparted to the thus obtained polyketone drawn yarn as necessary. The composition of the finishing agent can be selected as needed depending on the application and purpose, and the polyketone fiber can be improved in twist resistance, adhesion to rubber, resin, cement and the like, and imparted heat resistance.
[0042]
When the polyketone fiber of the present invention is used as a spun yarn, the polyketone fiber is crimped and cut into short fibers. Crimping can be imparted to the polyketone fiber in any step from spinning to spinning, but it is preferable to impart crimping after the end of stretching in terms of stretchability and obtained fiber properties. There is no limit to the method of imparting crimp, such as a method of pressurizing and bending under heating using a staffin box or the like, or a method of heat-treating a strain having a strain after the end of drawing without strain after cutting. Chemical, thermal and chemical treatments. In order to impart stable crimps, the treatment is preferably performed at 110 to 270 ° C, more preferably 150 to 250 ° C.
[0043]
As a method for cutting and spinning polyketone filaments into short fibers, known methods such as direct spinning, perlock method, converter method, and stapler method can be applied. The cutting method may be a method of cutting to a fixed length with a cutter, or cutting so that the short fiber length has a distribution by checking. Moreover, the method of heating a filament and carrying out heat | fever stretching and then checking into a short fiber may be used. When cutting by the check method, it is important to set the draft ratio and the check tension so that the average fiber length is 5 to 300 mm.
[0044]
The polyketone sliver obtained by the check-out is used as a spun yarn through the roving and spinning processes. There is no restriction | limiting about the method of twisting at the time of spinning, According to a use and the objective, it can be set as well-known twisted yarns, such as a twin yarn and a triple yarn. If necessary, they may be blended with fibers other than polyketone fibers such as polyester fibers, polyamide fibers, cellulose fibers, aramid fibers, polybenzazole fibers, polyvinyl alcohol fibers, acrylic fibers, polyethylene fibers, and polypropylene fibers. Although there is no restriction | limiting about a blending ratio, From the viewpoint of the intensity | strength and cost of spun yarn, the ratio of the polyketone fiber in spun yarn becomes like this. Preferably it is 50-100 mass%, More preferably, it is 70-100 mass%. There is no limitation on the number of twisted yarns, but if the number of twisted yarns is too large, the strength decreases due to twisting, and if the number of twisted yarns is small, the strength decreases by pulling out, so that the twisted yarn has the above twist coefficient (K) of 100. It is preferable to perform in the range of -3000, More preferably, it is 300-1000. From the viewpoints of the quality of the spun yarn and process passability, the twist tension is preferably 0.01 to 0.1 cN / dtex, more preferably 0.03 to 0.07 cN / dtex.
[0045]
When using the polyketone fiber of the present invention as a twisted yarn cord, there are no restrictions on the type, method, and number of twisted yarns, and any method such as single twisted yarn, cocoon twisted yarn, picco cocoon twisted yarn, strong twisted yarn is adopted, and the twisted yarn is used. The number of fibers to be used is not particularly limited, such as one twist or two twist, and may be three or more. The number of twisted yarns may be arbitrarily selected according to the application and use environment, but the twist coefficient (K) is preferably in the range of 1000 to 30000, more preferably 5500 to 15000. At this time, from the viewpoint of the quality of the obtained twisted yarn cord and handleability, it is preferable that the twisted yarn tension is 0.01 to 0.2 cN / dtex for both the lower twist and the upper twist.
[0046]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be specifically described with reference to examples and the like, but these do not limit the scope of the present invention.
The measuring method of each measured value used in the present invention is as follows.
(1) Intrinsic viscosity
The intrinsic viscosity [η] is determined based on the following definition formula.

“T” and “T” in the definition formula are the flow time of the viscosity tube at 25 ° C. of hexafluoroisopropanol having a purity of 98% or more and a polyketone diluted solution dissolved in hexafluoroisopropanol. C is the solute weight value in grams in 100 ml.
[0047]
(2) Fiber strength and elastic modulus
The tensile strength of the fiber is measured according to JIS-L-1013.
(3) Amount of adhesion of ionic compound and oil
The fiber is dried at 105 ° C. for 5 hours and weighed (W). The fiber is washed with warm water at 40 ° C. and then washed with ethyl ether at 25 ° C. to remove ionic compounds adhering to the fiber surface. After distilling off the ethyl ether, the fiber is dried at 105 ° C. for 5 hours and weight (W₀) And weigh the adhesion rate from the following formula.
Ionic compound adhesion rate = [(WW₀) / W₀] X 100 (%)
The same method is used for oil agents.
[0048]
(4) Crystallinity
Measurement is performed under the following conditions using a differential heat measuring device Pyris1 (trademark) manufactured by PerkinElmer Co., Ltd. The sample used is a fiber having a yarn length cut to 5 mm.
Sample mass: 1mg
Measurement temperature: 30 ° C → 300 ° C
Temperature increase rate: 20 ° C / min
Atmosphere: Nitrogen, flow rate = 200 mL / min
In the obtained endothermic curve, the degree of crystallinity is calculated from the following equation from the amount of heat ΔH (J / g) calculated from the area of the maximum endothermic peak observed in the range of 200 to 300 ° C.
Crystallinity = (ΔH / 225) × 100 (%)
[0049]
(5) Degree of crystal orientation
A fiber diffraction image is captured under the following conditions using an imaging plate X-ray diffractometer RINT2000 (trademark) manufactured by Rigaku Corporation.
X-ray source: CuKα ray
Output: 40KV 152mA
Camera length: 94.5mm
Measurement time: 3 minutes
From the half-value width H of the intensity distribution obtained by scanning the (110) plane observed in the vicinity of 2θ = 21 ° of the obtained image in the circumferential direction, the degree of crystal orientation is calculated by the following formula.
Crystal orientation = [(180−H) / 180] × 100 (%)
[0050]
(6) Average fiber length
It measures based on JIS-L-1015-7.4.1 (A method).
(7) Crimp degree
Measured based on JIS-L-1015-7.12.2.
(8) Stretchability
Within a 5-hour drawing time, the number of times a single yarn is wound around a yarn break, a drawing roll, or a guide is measured, and the drawability is evaluated according to the following criteria.
○: No yarn breakage or single yarn winding occurs
Δ: No yarn breakage, but single yarn winding occurs
×: Cut the yarn
[0051]
(9) Fluff
Visually inspect the surface of the wound package and measure the number of fluff.
○: No fluff is observed
Δ: 1 to 5 fluffs observed
X: 6 or more fluffs are observed
(10) Convergence
The yarn is pulled out from the package at a speed of 1 m / min, and the focused state of the drawn filament is determined according to the following criteria.
○: There is no dispersion of single yarns (one filament bundle)
Δ: Filament splits into 2 to 5 threads due to static electricity
×: Filament is divided into 6 or more yarns due to static electricity
(11) Rubber adhesion
Using unvulcanized rubber compounded with 70% by mass of natural rubber, 15% by mass of SBR and 15% by mass of carbon black, 1 cm of polyketone cord is embedded in this rubber, vulcanized under the conditions of 155 ° C., 3.5 MPa, 30 minutes, and then pulled out. Strength (N) is measured at a crosshead speed of 300 mm / min.
[0052]
[Example 1]
A polyketone having an intrinsic viscosity of 6.0 obtained by completely alternating copolymerization of ethylene and carbon monoxide prepared by a conventional method is dissolved in an aqueous solution containing 30% by mass of calcium chloride / 22% by mass of zinc chloride / 10% by mass of lithium chloride. Thus, a dope having a polyketone concentration of 6.5% by mass was obtained. The obtained dope was heated to 80 ° C., and after passing through an air gap of 10 mm from a nozzle with a nozzle diameter of 0.15 mmφ and a hole number of 250, 2% by mass of calcium chloride, 1.1% by mass of zinc chloride and It extruded into the coagulation bath which consists of water of -2 ° C. containing 0.1% by mass of hydrochloric acid.
[0053]
Subsequently, after the yarn was sequentially washed with an aqueous hydrochloric acid solution and water, 0.05% by mass of IRGANOX (registered trademark) 1098 (manufactured by Ciba Specialty Chemicals) and IRGANOX (registered trademark) 1076 (manufactured by Ciba Specialty Chemicals), respectively. After blending (with polyketone), it was dried at 225 ° C. for a fixed length.
A 10% by weight aqueous dispersion of cetyl phosphate potassium salt (monocetyl phosphate potassium salt / dicetyl phosphate potassium salt = 60% by weight / 40% by weight) was applied to the dried fiber by a dipping method, and subsequently 225 ° C./240. Four-stage drawing of 15.2 times in total at 6.5 / 1.5 / 1.3 / 1.2 times at ℃ / 250 ℃ / 257 ℃, respectively, to obtain a polyketone fiber with a total fineness of 252 dtex It was.
[0054]
The drawability was extremely good, and troubles such as winding of a single yarn and yarn breakage did not occur during drawing. The obtained polyketone fiber had high strength, no fluff or fibrils were observed, and had extremely high performance and high quality with excellent convergence.
The structures and properties of the polyketone fibers prepared in Examples 1 to 8 and Comparative Examples 1 to 7 of the present invention are shown in Tables 1 and 2 respectively. Table 1 also shows the structures and characteristics of the polyketone fibers after completion of the four-stage drawing used in the twisted yarn cords and spun yarns of Examples 9 to 11.
[0055]
[Example 2]
In Example 1, 10 mass% aqueous dispersion of stearyl phosphate potassium salt (monostearyl phosphate potassium salt / distearyl phosphate potassium salt = 50 mass% / 50 mass%) was added to the ionic compound to be applied to the polyketone fiber after drying. Spinning and drawing were performed in the same manner except that. The drawability was good, and the resulting polyketone fiber was also high performance and high quality.
[0056]
[Example 3]
In Example 1, an ionic compound to be imparted to the dried polyketone fiber is an octyl phosphate potassium salt (monooctyl phosphate potassium salt / dioctyl phosphate potassium salt = 45 mass% / 55 mass%) in an aqueous 10 mass% dispersion. Spinning and drawing were performed in the same manner except that. The drawability was good and the resulting polyketone fiber was also high performance and high quality.
[0057]
[Example 4]
In Example 1, the ionic compound to be applied to the dried polyketone fiber is the same except that it is a 10% by mass aqueous dispersion of alkylsulfonate sodium salt (alkyl is a mixture of linear saturated hydrocarbons of C10 to C15). Spinning and drawing. The drawability was good and the resulting polyketone fiber was also high performance and high quality.
[0058]
[Example 5]
Spinning was carried out in the same manner as in Example 1, except that the ionic compound to be added to the dried polyketone fiber was a 10% by mass aqueous dispersion of dipolyoxyethylene lauryl ether phosphate potassium salt (ethylene oxide 2 mol adduct). The film was stretched. The drawability was good and the resulting polyketone fiber was also high performance and high quality.
[0059]
[Example 6]
In Example 1, except that the ionic compound imparted to the polyketone fiber after drying was a 10 mass% aqueous dispersion of a monoisocetyl phosphate potassium salt / sodium monolaurate (= 60 mass% / 40 mass%) mixture. Spinning and drawing were performed in the same manner. The drawability was good and the resulting polyketone fiber was also high performance and high quality.
[0060]
[Example 7]
In Example 1, spinning and stretching were performed in the same manner except that the concentration of the ionic compound was 20% by mass as an aqueous dispersion and was applied in two stages after drying and after one-stage stretching. The drawability was good and the resulting polyketone fiber was also high performance and high quality.
[0061]
[Example 8]
Spinning and drawing were performed in the same manner as in Example 1 except that the concentration of the ionic compound was 2% by mass. The drawability was good and the resulting polyketone fiber was also high performance and high quality.
[0062]
[Example 9]
An ionic compound was applied in the same manner as in Example 1 except that the obtained 6 dried yarns were combined, and four-stage drawing was performed to obtain a multifilament having a fineness of 1655 dtex / 1500f. The process passability was very good, no fluff or yarn breakage occurred during stretching, and the strength was excellent.
The obtained polyketone fiber is twisted at 390 times / m in the Z direction (bottom twist tension: 0.05 cN / dtex), two of these are twisted, and twisted at 390 times / m in the S direction (top twist tension of 0). .05 cN / dtex) to produce a cord. The process passability at the time of twisting was good, the yarn was not wound around the fluff and the guide, and the obtained cord was excellent in quality with almost no fluff or fibrils. The strength of the twisted product is as high as 13.3 cN / dtex, and the cooperative utilization rate of twisted yarn (100 fraction obtained by dividing the cooperation of the cord after twisting by the strength of the fiber before twisting) is 75.1%. there were.
[0063]
[Example 10]
In Example 9, spinning, compounding, stretching, and twisting were performed in the same manner except that the polyketone fiber was wound by applying a finishing agent to the polyketone fiber at the end of four-stage stretching. A finishing agent having the following composition was used.
Oleic acid lauryl ester / bisoxyethyl bisphenol A / polyether (propylene oxide / ethylene oxide = 35/65: molecular weight 20000) / polyethylene oxide 10 mol addition oleyl ether / polyethylene oxide 10 mol addition castor oil ether / sodium stearylsulfonate / dioctyllin Sodium acid = 30/30/10/5/23/1/1 (mass% ratio).
[0064]
The adhesion rate of the finish was 1.8% by mass (vs. polyketone fiber). The twisting property was good, and troubles such as fluff and winding of single yarn did not occur during twisting.
The obtained cord is immersed in an RFL (resorcin-formalin-latex) solution having the following liquid composition, followed by a drying zone (heat treatment at 160 ° C. for 120 seconds at a tension of 3 N) and a heat set zone (220 at a tension of 4.2 N). RFL treatment code was obtained through a normalizing zone (heat treatment at 220 ° C. for 60 seconds at a tension of 2.8 N).
(RFL solution composition)
Resorcin 22.0 parts
Formalin (30% by mass) 30.0 parts
Sodium hydroxide (10% by mass) 14.0 parts
570.0 parts of water
Vinylpyridine latex (41% by mass) 364.0 parts
The obtained RFL resin-adhered polyketone cord had a high twist strength utilization rate of 73.5% and an extremely high adhesive strength to rubber of 165 N / cm / cord.
[0065]
Example 11
In Example 1, spinning and drawing were carried out in the same manner except that the ionic compound was added after twelve dry yarns were combined, and polyketone fibers having a total fineness of 3150 detex were obtained. The obtained polyketone fiber was crimped with an indentation type crimping machine, then heat-set at 220 ° C., then cut into short fibers with a rotary cutter, single yarn fineness 0.9 dtex, average fiber length 71 mm Polyketone short fibers were obtained.
This polyketone short fiber was formed into a sliver shape, and a single twist (Z twist) of 750 T / m was added to produce a spun yarn having a fineness of 120 dtex. The process passability at the time of spinning is good, there are no problems such as dirt or tangling of single yarn due to adhesion of yarn waste or oil to the card, and the obtained spun yarn has a tensile strength of 7.5 cN / dtex. It was of high strength.
[0066]
[Comparative Example 1]
In Example 1, it extended | stretched similarly except not giving an ionic compound. The spread of the yarn bundle due to static electricity was observed on the roll and the guide immediately after the first stage drawing, and the single filaments of adjacent filaments overlapped on the three-stage drawn feed roll, resulting in single yarn breakage. Although the obtained fiber was high in strength, it had poor yarn unwindability due to repulsion due to static electricity, and was inferior in quality with a lot of fluff and fibrils.
[0067]
[Comparative Example 2]
In Example 1, mineral oil (paraffin wax having a redwood viscosity of 100 seconds) was applied in place of the ionic compound. Smoke from the yarn bundle was observed during the first and second stretches. The drawability was poor, the yarn bundle was expanded due to static electricity, and single yarn breakage occurred due to single yarn overlap on the roll. Although the obtained fiber had high strength, it had many fuzz and was of poor quality.
[0068]
[Comparative Example 3]
In Example 1, polyoxyethylene lauryl ether (EO 20 mol adduct) was added instead of the ionic compound. The drawability was poor, and the yarn breakage occurred in the second stage of the multi-stage drawing, and it was not possible to carry out a high magnification drawing.
[0069]
[Comparative Example 4]
In Example 1, sorbitan monostearate / polyoxyethylene stearyl ether (EO 20 mol adduct) / polyoxyethylene oleyl ether (EO 3 mol adduct) = (37.5 / 25 / 37.5) instead of ionic compound Mass%). The drawability was poor, and the yarn was broken at the third stage of the multistage drawing, and the drawing at a high magnification could not be performed.
[0070]
[Comparative Example 5]
In Example 1, an oil agent having the following composition was applied instead of the ionic compound.
Oleic acid lauryl ester / bisoxyethyl bisphenol A / polyether (propylene oxide / ethylene oxide = 35/65: molecular weight 20000) / polyethylene oxide 10 mol addition oleyl ether / polyethylene oxide 10 mol addition castor oil ether / sodium stearylsulfonate / dioctyllin Sodium acid = 30/30/10/5/23/1/1 (mass% ratio).
Although there was no yarn breakage at the time of drawing, a single yarn was wound around the guide. Moreover, the fiber after four-stage drawing was colored brown and single yarns were stuck. The strength of the obtained fiber was reduced by 10% or more compared to Example 1.
[0071]
[Comparative Example 6]
In Example 1, oleylamine acetate was added in place of the ionic compound. The drawability was poor, and the yarn breakage occurred in the second stage of the multi-stage drawing, and it was not possible to carry out a high magnification drawing.
[0072]
[Comparative Example 7]
In Example 1, spinning and stretching were performed in the same manner except that the ionic compound to be added was added in two stages as an aqueous dispersion having a concentration of 40% by mass. The obtained drawn yarn was colored brown, and precipitation of a white product was observed on the guide and the roll.
[0073]
[Table 1]

[0074]
[Table 2]

[0075]
【The invention's effect】
The polyketone fiber of the present invention is excellent in antistatic properties, bundling properties, and wear resistance. Further, in production, it is excellent in process passability during stretching, and further in strength, quality, handleability, and process passability in post-processing.
The polyketone fiber of the present invention has excellent performance and quality even for industrial material applications with a large number of filaments. It is particularly useful for clothing materials such as spun yarn.

Claims (7)

95-100% by mass of the repeating unit is a polyketone fiber composed of 1-oxotrimethylene, and at least one ionic compound selected from the group consisting of the following (a) to (d) is contained in the polyketone fiber: 0 to 30% by mass with respect to the total adhesion amount of the ionic compounds (a) to (d) in which 0.05 to 1% by mass of the oil component other than the following (a) to (d) is adhered. % Polyketone fiber.
(A) R ¹ —P (═O) (OX ¹ ) (OX ² )
(B) R ² —P (═O) (O—R ³ ) (OX ³ )
(C) R ⁴ —S (═O) (OX ⁴ )
(D) R ⁵ —C (═O) (OX ⁵ )
(In the formula, X ^{1 to} X ⁵ are at least one selected from the group consisting of hydrogen, alkali metals, alkaline earth metals, and NH ₄ , and R ^{1 to} R ⁵ are organic having 3 to 30 carbon atoms. Base) X ^{1 to} X ⁵ constituting the ionic compounds (a) to (d) are potassium or sodium, and R ^{1 to} R ⁵ are hydrocarbon groups having 4 to 18 carbon atoms. The polyketone fiber according to claim 1.   The repeating unit is composed of a polyketone in which 97 to 100% by mass is 1-oxotrimethylene, has a crystallinity of 60% or more and a crystal orientation of 90% or more. The polyketone fiber described.   The polyketone fiber is a multifilament having a single yarn number of 100 or more, and has a strength of 12 cN / dtex or more and an elastic modulus of 250 cN / dtex or more. The polyketone fiber described in 1.   The polyketone fiber according to any one of claims 1 to 3, wherein the polyketone fiber is a short fiber having an average fiber length of 5 to 300 mm. Spinning containing 50% by mass or more of a polyketone fiber comprising a polyketone in which 95 to 100% by mass of the repeating unit is 1-oxotrimethylene, an average fiber length of 10 to 200 mm, and a degree of crimp of 5 to 50%. It is a thread | yarn, Comprising: At least 1 sort (s) of ionic compound chosen from the group which consists of following (a)-(d) adheres 0.05-1 mass% with respect to spun yarn, and following (a)-( The spun yarn, wherein the amount of the oil component other than d) is 0 to 30% by mass with respect to the total amount of the ionic compounds (a) to (d).
(A) R ¹ —P (═O) (OX ¹ ) (OX ² )
(B) R ² —P (═O) (O—R ³ ) (OX ³ )
(C) R ⁴ —S (═O) (OX ⁴ )
(D) R ⁵ —C (═O) (OX ⁵ )
(Wherein, X ^{1 to} X ⁵ are at least one selected from the group consisting of hydrogen, alkali metals, alkaline earth metals, and NH ₄ , and R ^{1 to} R ⁵ have 3 to 30 carbon atoms. Is an organic group) A twisted cord in which 95 to 100% by mass of the repeating unit is made of polyketone fiber having 1-oxotrimethylene, and is twisted in a range of a twist coefficient (K) of 1000 to 30000 represented by the following formula, At least one ionic compound selected from the group consisting of (a) to (d) is attached to 0.05 to 1% by mass with respect to the twisted cord, and oil components other than the following (a) to (d) The twisted yarn cord is characterized in that the adhering amount is 0 to 30% by mass with respect to the total adhering amount of the ionic compounds (a) to (d).
K = Y × D ^0.5
(Where Y is the number of twists per meter (T / m), and D is the total fineness (dtex) of the polyketone fibers used in the twisted yarn)
(A) R ¹ —P (═O) (OX ¹ ) (OX ² )
(B) R ² —P (═O) (O—R ³ ) (OX ³ )
(C) R ⁴ —S (═O) (OX ⁴ )
(D) R ⁵ —C (═O) (OX ⁵ )
(In the formula, X ^{1 to} X ⁵ are at least one selected from the group consisting of hydrogen, alkali metals, alkaline earth metals, and NH ₄ , and R ^{1 to} R ⁵ are organic having 3 to 30 carbon atoms. Base)