JP3636335B2 - High salt water absorbable fiber - Google Patents

Description

【００１２】
また、化２におけるＸがアミド基、Ｒ₃ 及びＲ₄ がメチル基、Ｒ₅ が炭素数１から３のアルキレン基である（メタ）アクリルアミド型のカルボキシベタイン型単量体を両イオン性ビニル系単量体（Ａ）として用いることにより、さらに高度に電解質水溶液吸収性の繊維を得ることができる。すなわち、単量体側鎖基中に導入された親水性の強いアミド結合の存在により重合体の親水性が上がるために吸収能力が向上する。
【００１３】
カルボキシベタイン型単量体は多くの場合、対応する３級アミン型単量体とモノハロアルキルカルボン酸類との反応によって合成することができる。例えば、ジメチルアミノエチルメタクリレートとモノクロロ酢酸ナトリウムをメタノール中で反応させることによってＮ，Ｎ−ジメチル−Ｎ−（２−メタクリロイルオキシエチル）−Ｎ−（カルボキシメチル）アンモニウム内部塩が合成できる。また、３級アミン型単量体とプロピオラクトン等の環状エステルとの反応によっても本発明の両イオン性ビニル系単量体（Ａ）を合成することができる。その他、Ｎ，Ｎ−ジメチル−Ｎ−（２−メタクリロイルオキシエチル）−Ｎ−（カルボキシエチル）アンモニウム内部塩、Ｎ，Ｎ−ジメチル−Ｎ−（２−アクリロイルオキシエチル）−Ｎ−（カルボキシメチル）アンモニウム内部塩、Ｎ，Ｎ−ジメチル−Ｎ−（２−アクリロイルオキシエチル）−Ｎ−（カルボキシエチル）アンモニウム内部塩等のカルボキシベタイン型単量体が本発明における両イオン性ビニル系単量体（Ａ）として好適に使用することができる。
【００１４】
また、両イオン性ビニル系単量体（Ａ）として、Ｎ，Ｎ−ジメチル−Ｎ−（３−アクリルアミドプロピル）−Ｎ−（カルボキシメチル）アンモニウム内部塩、Ｎ，Ｎ−ジメチル−Ｎ−（３−メタクリルアミドプロピル）−Ｎ−（カルボキシメチル）アンモニウム内部塩、Ｎ，Ｎ−ジメチル−Ｎ−（３−アクリルアミドプロピル）−Ｎ−（カルボキシエチル）アンモニウム内部塩、Ｎ，Ｎ−ジメチル−Ｎ−（３−メタクリルアミドプロピル）−Ｎ−（カルボキシエチル）アンモニウム内部塩等の（メタ）アクリルアミド型のカルボキシベタイン型単量体が本発明においてさらに好適に使用することができる。
【００１５】
本発明は重合体及びそれからなる繊維に対する高分子反応によって両イオン性官能基を該重合体及び繊維中に導入した場合も包含する。すなわち、３級アミノ基を有する重合体／繊維とモノハロアルキルカルボン酸類との高分子反応によって両イオン性官能基を導入する方法、あるいは重合体／繊維と両イオン性官能基を有する化合物との反応によって導入する方法、重合体／繊維に両イオン性ビニル系単量体（Ａ）をグラフト重合する方法等の採用によっても電解質水溶液に対して高度に吸収性である繊維を得ることができる。
【００１６】
共重合体（Ｉ）中に両イオン性ビニル系単量体（Ａ）を１０重量％〜９９重量％の範囲内で共重合成分として含有することによって、本発明の課題である電解質水溶液に対して高度に吸収性である繊維が得られる。両イオン性ビニル系単量体（Ａ）が１０重量％未満では十分な電解質水溶液吸収性が得られないため、両イオン性ビニル系単量体（Ａ）は１０重量％以上、好ましくは２０重量％以上であることが望ましい。
【００１７】
本発明において、共重合体（Ｉ）中に両イオン性ビニル系単量体（Ａ）以外の単量体を繊維物性を向上させる等の理由により使用することができ、繊維の吸収性能を妨げない範囲内ではその種類に制限はない。すなわち、使用目的に合わせて重合体の強度等の物性を改良する等の理由でラジカル重合性のビニル系単量体の中から１種以上を適宜選択し使用することができる。特に繊維に可塑性、柔軟性、強靱性を付与するために可塑化単量体（Ｂ）を使用することが望ましい。
【００１８】
かかる可塑化単量体（Ｂ）としては、アクリロニトリル、メタクリロニトリル、酢酸ビニル、塩化ビニル、塩化ビニリデン、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、プロピルアクリレート、プロピルメタクリレート、ブチルアクリレート、ブチルメタクリレート、スチレン等のラジカル重合性単量体が好適に使用することができる。
【００１９】
特に可塑化単量体（Ｂ）の少なくとも１成分としてアクリロニトリルを使用することにより、本発明の繊維に良好な物性を付与することができる。すなわち、アクリロニトリルを共重合することにより、共重合体（Ｉ）に柔軟性と物理的強度及び低吸湿性を付与することができ、さらに吸水後のゲル強度も向上させることができる。
【００２０】
共重合体（Ｉ）中に１０重量％〜４０重量％の範囲内で少なくとも１種類以上の可塑化単量体（Ｂ）を共重合成分として含有させることにより、繊維物性が向上する。ただし、可塑化単量体（Ｂ）の共重合体（Ｉ）中の組成が高いほど繊維物性の向上が図れるが、繊維の吸水性能を大きく低下させないために４０重量％以下、好ましくは３５重量％以下であることが望ましい。また、可塑化単量体（Ｂ）の組成が低いと十分な繊維物性が得られ難いため、１０重量％以上、好ましくは２０重量％以上であることが望ましい。
【００２１】
また、繊維の吸収性能を向上させる、繊維物性を改良する、架橋成分として使用する、製造原価を低下させる等の理由により、親水性単量体（Ｃ）を共重合体（Ｉ）中に含有させることは、塩水に対する吸収性能を極端に低下させない範囲内において推奨される。この様な親水性単量体（Ｃ）としては、カルボキシル基、アミド基、水酸基、スルホン酸基、リン酸基、アミノ基、４級アンモニウム基、ポリエチレングリコール基等の親水性の官能基を有するビニル系単量体が挙げられる。また、加水分解等により容易に親水性官能基を導入しうる単量体も同様に使することができる。
【００２２】
この様な親水性官能基を有する、及び導入可能な単量体としては例えば、アクリル酸及びそのアルカリ塩、メタクリル酸及びそのアルカリ塩、イタコン酸、アクリロニトリル、アクリル酸アルキルエステル、メタクリル酸アルキルエステル、アクリルアミド、メタクリルアミド、Ｎ−置換アルキルアクリルアミド、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシエチルアクリルアミド、酢酸ビニル、ビニルスルホン酸及びそのアルカリ塩、メタアリルスルホン酸及びそのアルカリ塩、スチレンスルホン酸及びその塩、２−アクリルアミド−２−メチルプロパンスルホン酸及びそのアルカリ塩、２−メタクリロイルオキシエタンスルホン酸及びそのアルカリ塩、モノ（２−アクリロイルオキシエチル）アシッドホスフェート、モノ（２−メタクリロイルオキシエチル）アシッドホスフェート、３−メタクリルアミドプロピルジメチルアミン及びその塩、２−メタクリロイルオキシエチルジメチルアミン及びその塩、２−メタクリロイルオキシエチルジエチルアミン及びその塩、３−メタクリルアミドプロピルトリメチルアンモニウムクロライド、Ｎ−ビニル−２−ピロリドン、ポリエチレングリコールメタクリレート、ポリエチレングリコールアクリレート等があり、これらの単量体を１種または２種以上組み合わせて使用することができる。
【００２３】
親水性単量体（Ｃ）の共重合体（Ｉ）中の組成は、電解質水溶液に対する高吸収性を発現させるために７０重量％以下、好ましくは１０重量％〜５０重量％の範囲内であることが望ましい。
【００２４】
吸水樹脂あるいは吸水繊維が水性媒体を吸収し、媒体に溶解する事無く膨潤状態を維持するためには、共有結合、静電結合、あるいは水素結合等によって重合体に架橋構造を導入することが必要である。本発明において共重合体（Ｉ）に架橋構造を導入するために、架橋性単量体（Ｄ）としてジビニル化合物の様な多官能ラジカル重合性単量体を用いることができるが、その場合、重合後に繊維状に成形することは事実上不可能であり、重合と同時に成形が行われる必要がある。例えば、単量体組成物を毛細管に注型した後、その状態で重合し繊維化する様な注型重合法が採用される。
【００２５】
多官能ラジカル重合性単量体としては、ビスアクリルアミド類、ジ（メタ）アクリル酸エステル類、ジアリル化合物類等が挙げられ、具体的には、Ｎ，Ｎ−ジアリルメタクリルアミド、ジアリルアミン、Ｎ，Ｎ−ビスアクリルアミド酢酸、Ｎ，Ｎ’−ビスアクリルアミド酢酸メチルエステル、Ｎ，Ｎ’−メチレンビスアクリルアミド、Ｎ，Ｎ−ベンジリデンビスアクリルアミド、ジアリルスクシネート、エチレングリコールジアクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、１，６−ヘキサンジオールジアクリレート、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、１，４−ブタンジオールジメタクリレート、１，３−ブタンジオールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、２−ヒドロキシ−３−アクリロイルオキシプロピルメタクリレート、グリセリンジメタクリレート、ネオペンチルグリコールジメタクリレート、ジアリルアクリルアミド等があり、本発明において使用することができる。
【００２６】
この様な多官能ラジカル重合性単量体の共重合体（Ｉ）中の組成は、水性媒体を吸収した重合体が媒体に溶解せず、且つ流動性あるいは粘着性を持たないために、好ましくは０．０１重量％以上であることが望ましい。また、多官能ラジカル重合性単量体の組成が高くなると吸収能力が低下してしまうため、１重量％以下、好ましくは０．１重量％以下の組成であることが望ましい。
【００２７】
重合体に架橋構造を導入する他の方法として、重合後後架橋可能な官能基を有する単量体の架橋化処理がある。すなわち、共重合体（Ｉ）の組成物を繊維状に成形した後、架橋化処理を行い架橋構造を導入する方法である。本発明において架橋化処理可能な、すなわち後処理により架橋構造を導入することが可能な単量体を架橋性単量体（Ｄ）として採用するときは、単量体（Ｄ）と化学的に結合し架橋構造を形成するような化合物を用いる場合があり、この化合物を架橋助剤と称する。また、熱処理等によって自己架橋する様な単量体を用いる場合は架橋助剤は必ずしも必要としない。
【００２８】
尚、架橋性単量体（Ｄ）は親水性単量体（Ｃ）と同一の単量体であってもよく、その場合、架橋性単量体（Ｄ）は親水性単量体（Ｃ）中の架橋化処理後の架橋構造に寄与した単量体成分と見なす。
【００２９】
かかる架橋構造を導入可能な単量体としては、カルボキシル基、アミド基、ニトリル基、メチロール基、グリシジル基、水酸基、イミノ基を含有する単量体、酸無水物系単量体が本発明において好適に使用することができる。例えば、アクリル酸、メタクリル酸、イタコン酸、アクリルアミド、メタクリルアミド、アクリロニトリル、Ｎ−メチロールアクリルアミド、グリシジルアクリレート、グリシジルメタクリレート、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシエチルアクリルアミド、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、イミノールメタクリレート等が挙げられる。
【００３０】
架橋助剤としては例えば、架橋性単量体（Ｄ）がカルボキシル基を有する場合には、水酸基、エポキシ基、アミノ基、メチロール基等のカルボキシル基と反応して化学結合を形成しうる官能基を２個以上有する多官能性化合物、例えば、エチレングリコール、プロピレングリコール、グリセリン、グリシジルアルコール、ジグリシジルエーテル、グリセリントリグリシジルエーテル、エチレングリコールジグリシジルエーテル、エタノールアミン、エチレンジアミン、プロピレンジアミン、ポリエチレングリコール、ポリビニルアルコール、トリメチロールメラミン、ペンタエリスリトール、トリメチロールプロパン、ポリエチレンイミン、尿素等が挙げられる。また、ホルムアルデヒドによる架橋化も挙げられる。さらに、カルボキシル基と化学結合を形成しうる官能基を有する単量体を架橋性単量体（Ｄ）として、カルボキシル基を有する単量体と共に併用して架橋化することもできる。
【００３１】
架橋性単量体（Ｄ）が水酸基を有する場合には、カルボキシル基、酸無水物、アルデヒド基、イソシアネート基の様な水酸基と反応して化学結合を形成し得る官能基を２個以上有する多官能性化合物、例えば、マロン酸、コハク酸、グルタル酸、リンゴ酸、プロパン−１，２，３−トリカルボン酸及びそれらの酸無水物、グリオキザール、グルタルアルデヒド、ヘキサメチレンジイソシアネート、シクロヘキサンジイソシアネート等が架橋助剤として挙げられる。さらに、水酸基と化学結合を形成しうる官能基を有する単量体を架橋性単量体（Ｄ）として、水酸基を有する単量体と共に併用して架橋化することもできる。
【００３２】
また、水酸基が水酸基同志、あるいはカルボキシル基と水素結合により架橋構造を形成する様な場合は架橋助剤を使用する必要はない。例えば、可塑化単量体（Ｂ）として酢酸ビニルあるいは（メタ）アクリル酸エステル等を用い、エステルの加水分解により水酸基あるいはカルボキシル基を生成させれば、熱処理によって水素結合性の微結晶構造を架橋点として、特に共有結合による架橋構造を導入しなくとも水性媒体を吸収し膨潤状態を維持することができ、この様な架橋構造の導入方法も本発明において採用することができる。
【００３３】
また、カルボキシル基同志、カルボキシル基と水酸基、あるいは水酸基同志を脱水触媒を用いて、酸無水物を形成することによる架橋化、エステル結合による架橋化、あるいはエーテル結合による架橋化を行うことによっても架橋構造を導入することができる。
【００３４】
架橋性単量体（Ｄ）がニトリル基を有する場合には、アミノ基の様なニトリル基と反応して化学結合を形成しうる官能基を２個以上有する多官能性化合物、例えば、ヒドラジン、エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、両末端アミノ化ポリエチレングリコール等が架橋助剤として挙げられる。さらに、ニトリル基と化学結合を形成しうる官能基を有する単量体を架橋性単量体（Ｄ）としてニトリル基を有する単量体と共に併用して架橋化することもできる。
【００３５】
これらの後架橋性を有する架橋性単量体（Ｄ）を１種または２種以上用いて共重合体（Ｉ）を合成し、重合後任意の方法により繊維状に成形した後、架橋化処理を行い架橋構造を導入するという方法により容易に本発明の高塩水吸収性繊維が作製できる。尚、本発明における架橋化処理は用いた架橋性単量体（Ｄ）の種類に応じて適宜選択すればよいが、乾熱処理による方法が好適に採用される。
【００３６】
特に、カルボキシル基を有する単量体と水酸基を有する単量体を架橋性単量体（Ｄ）として併用し、共重合体（Ｉ）の組成物を繊維状に成形した後、架橋構造を導入する方法は、架橋化処理の容易さ、処理条件の設定範囲が広いことから本発明においてさらに好適に採用される。
【００３７】
本発明の共重合体（Ｉ）は従来より行われているラジカル重合法のいずれの方法を用いて調整してもよい。すなわち、塊状重合、水系沈殿重合、懸濁重合、逆相懸濁重合、乳化重合、溶液重合のいずれの方法を用いてもよく、目的に応じて、得られる重合体の形態を考慮して適宜選択すればよい。しかし、一般には水を媒体とした重合系がコスト、環境面から望ましい。ラジカルの発生方法はラジカル重合触媒を用いる方法、放射線、電子線、紫外線を照射する方法等が挙げられる。ラジカル重合触媒としては例えば、過酸化水素、過酸化ベンゾイル、クメンハイドロパーオキサイド等の過酸化物、アゾビスイソブチロニトリル、アゾビスシアノ吉草酸等のアゾ化合物、過硫酸アンモニウム、過硫酸カリウム等の過硫酸塩等のラジカル発生剤、及びこれらのラジカル発生剤と亜硫酸水素ナトリウム、Ｌ−アスコルビン酸等の還元剤との組み合わせからなるレドックス系開始剤が挙げられる。重合媒体としては例えば、水、電解質水溶液、メタノール、アセトン、ジメチルホルムアミド等が挙げられるが、重合方法に応じて適宜選択すればよい。
【００３８】
本発明において繊維中に共重合体（Ｉ）と共に、ポリビニルアルコール、ポリエチレングリコール、ポリエチレンオキサイドから選ばれる１種以上の可塑化重合体（ＩＩ）を含有させることにより、繊維強度、吸湿時の低粘着性等の繊維物性を飛躍的に向上させることができる。また、ポリビニルアルコールの様な水酸基を多数有する重合体は、共重合体（Ｉ）中に水酸基と反応して化学結合を形成するような官能基を有する単量体を架橋性単量体（Ｄ）として採用していれば、架橋化処理により架橋構造を形成することができるため、吸水時に可塑化重合体（ＩＩ）が溶出しないという利点も併せ有する。尚、ポリビニルアルコールの重合度及びケン化度、ポリエチレングリコール及びポリエチレンオキサイドの重合度は繊維物性、吸収性能、繊維への成形性等を考慮して目的に応じて適宜選択すればよい。特に、可塑化重合体（ＩＩ）としてポリビニルアルコールを用いると繊維強度が大きく向上し、吸湿性が大きく低下するため、本発明においてさらに好ましい。
【００３９】
これらの可塑化重合体（ＩＩ）の繊維中の組成は、良好な繊維物性を発現させるために５重量％以上であることが望ましい。また、繊維の吸収性能を大きく低下させないために２０重量％以下、好ましくは１５重量％以下の組成であることが望ましい。
【００４０】
本発明における繊維の作製方法としては、前述した注型重合法と通常の紡糸方法があるが、本発明においては通常の紡糸法による繊維化がより好適に採用される。紡糸法としては、共重合体（Ｉ）の溶液を原液とした湿式紡糸法、乾湿式紡糸法、乾式紡糸法のいずれの紡糸方法も採用できる。また、繊維の構造としては、芯鞘構造、海島構造、サイドバイサイド構造等の複合構造も好適に採用することができ、目的に応じて適宜選択すればよい。例えば、芯部にポリビニルアルコール、鞘部に本発明の共重合体（Ｉ）の架橋性組成物を有する芯鞘構造の繊維とすれば、高吸収性と共に非常に優れた繊維物性を有する極めて優秀な繊維が得られる。
【００４１】
湿式紡糸法及び乾湿式紡糸法では、共重合体（Ｉ）と必要に応じて可塑化重合体（ＩＩ）及び必要に応じて各種添加剤を適当な溶媒に溶解し適当な粘度に調整して原液とし、貧溶媒中に多孔ノズルから紡出し、必要に応じて延伸した後、架橋化処理することにより本発明の高塩水吸収性繊維が製造できる。この時、溶媒としては、例えば水、メタノール、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド等が挙げられ、これらを単独、あるいは複合して使用することができる。貧溶媒としては、例えばアセトン、メチルエチルケトン、トルエン、酢酸エチル、ヘキサン等が挙げられ、これらを単独又は混合して、あるいは溶媒と複合して使用することもできる。
【００４２】
乾式紡糸法では、共重合体（Ｉ）と必要に応じて可塑化重合体（ＩＩ）及び必要に応じて各種添加剤を適当な溶媒に溶解し適当な粘度に調整して原液とし、加熱雰囲気中に紡出して溶媒を蒸発させ、必要に応じて延伸操作を行い、その後架橋化処理することにより本発明の高塩水吸収性繊維を製造することができる。溶媒としては、例えば水、メタノール、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド等が挙げられ、これらを単独、あるいは複合して使用することができる。本発明においては、特に水を溶媒とした乾式紡糸法による繊維化がコスト、安全性、作業環境等の利点から特に好ましい。
【００４３】
以下、乾式紡糸法を用いた本発明の高塩水吸収性繊維の作製法について説明する。紡糸原液としては、水を溶媒とした重合系で、重合した後の溶液がそのまま原液となるものが好ましい。共重合体（Ｉ）及び必要に応じて添加される可塑化重合体（ＩＩ）の原液中での濃度は、紡糸に適した粘度になるように調整する必要があり、一般的には１５重量％〜５０重量％、好ましくは１８重量％〜２５重量％である。原液の粘度は、加熱雰囲気中での伸長粘度が十分にあり糸切れせずに安定した紡糸が可能であれば特に制限はないが、一般的には２５℃におけるＢ型粘度計での粘度が１００ポイズ〜４０００ポイズの範囲内である。
【００４４】
原液の紡出温度は一般的には３０℃〜８０℃の範囲内である。加熱雰囲気の温度は使用する溶媒に応じて適宜選択すればよいが、一般的には１００℃〜３００℃、好ましくは１５０℃〜２５０℃に設定するのがよい。尚、乾燥工程の後に繊維を延伸する場合、加熱雰囲気から出た時の繊維の溶媒分率を１０重量％〜１５重量％程度に設定することにより延伸工程が円滑に行える。繊維の延伸倍率は良好な繊維物性を付与する様に適宜設定すればよいが、一般的には１．５倍〜１０倍程度である。
【００４５】
繊維に架橋構造を付与するための架橋化処理は、本発明において乾熱処理による方法が好適に採用される。すなわち、共重合体（Ｉ）中の架橋性単量体（Ｄ）として熱処理によって架橋構造を形成する様な単量体を１種以上採用する。この時、可塑化重合体（ＩＩ）も同時に架橋構造を形成することが望ましい。乾熱処理の温度は、所望の時間で架橋化ができる様に設定すればよいが、一般的には１５０℃〜３００℃の範囲内である。尚、架橋化処理の条件（温度、時間）を変更する事により繊維の吸収性能を制御することができ、所望の性能に応じて、条件を適宜設定すればよい。但し、架橋構造が少なすぎる場合、吸水した繊維からの重合体の溶出が多くなるため注意する必要がある。
【００４６】
最終繊維の直径は一般的には、５〜１００μｍ、好ましくは１５〜５０μｍ程度である。繊維原綿は連続したフィラメント状、あるいは適当な長さに切断したステープル状の形態で供され、そこから必要に応じて、ヤーン、不織布、各種成形体、エレメント等に加工され、使用される。
【００４７】
【作用】
本発明の高塩水吸収性繊維が電解質水溶液に対して高度に吸収性である理由は十分に解明するに至っていないが、以下のことが言える。すなわち、架橋していない線状のカルボキシベタイン型モノマーの単独重合体が純水だけでなく電解質水溶液に対しても良溶解性を示し、さらに高濃度の電解質水溶液及び多価イオンを含有する電解質水溶液に対しても優れた溶解性を示すことから、架橋構造を有する重合体においても電解質水溶液に対して膨潤し、高吸収性を示す。従って、その様な重合体を含有する繊維も電解質水溶液に対して高吸収性を示す。
【００４８】
【実施例】
以下、実施例に従って本発明を具体的に説明するが、本発明の範囲がこれら実施例にのみ限定されるものではない。
【００４９】
実施例１
本実施例において両イオン性ビニル系単量体（Ａ）として、Ｎ，Ｎ−ジメチル−Ｎ−（３−アクリルアミドプロピル）−Ｎ−（カルボキシメチル）アンモニウム内部塩（以下、ＤＡＰＭＢと略す）は興人株式会社から入手した。また、Ｎ，Ｎ−ジメチル−（３−メタクリルアミドプロピル）−Ｎ−（カルボキシメチル）アンモニウム内部塩（ＤＭＰＭＢ）、Ｎ，Ｎ−ジメチル−Ｎ−（２−メタクリロイルオキシエチル）−Ｎ−（カルボキシメチル）アンモニウム内部塩（ＤＭＥＭＢ）は各単量体の対応する３級アミン型単量体とモノクロロ酢酸ナトリウムをメタノール中、６０℃で反応させることにより合成した。
【００５０】
可塑化単量体（Ｂ）としてはアクリロニトリル（ＡＮ）、メチルアクリレート（ＭＡ）を用いた。親水性単量体（Ｃ）としてはアクリル酸（ＡＡ）、ヒドロキシエチルアクリレート（ＨＥＡ）を用いた。また、後架橋性を有する架橋性単量体（Ｄ）として、単量体（Ｃ）であるＡＡとＨＥＡとを併せて使用した。また、Ｎ−メチロールアクリルアミド（ＮＭＡＭ）も親水性単量体（Ｃ）であるが、架橋性単量体（Ｄ）としても使用した。尚、ＡＡは全てＮａＯＨ水溶液を用いて添加量の約７０モル％を中和してから重合に使用した。可塑化重合体（ＩＩ）としては、ポリビニルアルコール（ＰＶＡ−２１７（平均重合度：１７００、鹸化度：８８％）及びＰＶＡ−２０５（重合度：５００、鹸化度：８８％）、クラレ（株）製）及びポリエチレングリコール（ＰＥＧ−６０００及びＰＥＧ−２００００、和光純薬工業（株）製）を用いた。
【００５１】
共重合体（Ｉ）は、所定量の各種単量体を蒸留水に溶解あるいは懸濁させ、開始剤として総単量体重量に対し０．８重量％の過硫酸カリウム（ＫＰＳ）を添加し、７０℃で５時間攪拌下に重合した。また、開始剤としてＫＰＳと亜硫酸水素ナトリウム（ＳＨＳ）からなるレドックス系を用いた場合は、６０℃で５時間攪拌下に重合した。この時、ＫＰＳは総単量体重量に対し０．８重量％使用し、ＳＨＳはＫＰＳに対し１．２モル等量を数回に分割して添加した。また、可塑化重合体（ＩＩ）を添加した系も同様に、所定量の可塑化重合体（ＩＩ）を添加して重合を行った。重合した溶液を減圧下に脱泡し、そのまま原液として使用した。原液固形分は、原液約１ｇを１２０℃で４時間乾燥して乾燥体の重量を測定して求めた。原液の粘度はビスメトロン粘度計（芝浦システム（株）製）を用い２５℃で測定した。尚、比較のために両イオン性ビニル系単量体（Ａ）を含まない共重合体も同様に重合し、原液とした。表１に各種組成で重合した原液の単量体仕込み組成と可塑化重合体（ＩＩ）の添加量及び原液の固形分、原液粘度を示す。
【００５２】
【表１】

【００５３】
乾式紡糸は定法に従って行った。原液を多孔ノズルから約２００℃の加熱雰囲気中に紡出し、約２倍に延伸して巻き取った。その後、２００℃で１〜５分緊張下に乾熱処理を行い、乾燥繊維を得た。乾熱処理の時間は、繊維が水性媒体を吸収した後に溶解しないように設定した。得られた繊維を約１００ｍｍに切断し、以下の各種評価に供した。
【００５４】
繊維の引張強度、伸度はＪＩＳ Ｌ １０１５に記載の方法に準じて測定した。繊維のデニールは繊維重量と繊維長から計算により求めた。繊維の吸収性能は、以下の方法によって純水及び各種電解質水溶液に対する吸収倍率を測定し評価した。乾燥した繊維１ｇを純水及び各種電解質水溶液５００ｍｌ中に２時間浸漬した後、２００メッシュ金網で濾過し、１０分間水切りした後、金網上の水性媒体を吸収した膨潤繊維の重量を測定し、繊維１ｇ当たりの吸収した水性媒体のグラム数を吸収倍率とした。電解質水溶液としては、０．９重量％のＮａＣｌ水溶液、１０重量％のＮａＣｌ水溶液、５重量％のＣａＣｌ₂ 水溶液、人工海水（アクアマリンＳ、八州薬品（株）製）を用いた。また、比較のために市販品である高吸水性繊維（ランシールＦ、東洋紡績（株）製）も同様に評価した。表２に各繊維の強伸度及び各種水性媒体に対する吸収倍率を示す。
【００５５】
【表２】

【００５６】
繊維１は両イオン性ビニル系単量体（Ａ）であるＤＡＰＭＢと架橋性単量体（Ｄ）であるＮＭＡＭとの共重合体からなる繊維であり、繊維物性は低いがその吸収倍率は純水、及び各種電解質水溶液ともに高く非常に優れたものであった。特に、高濃度の電解質水溶液及び多価イオンを高濃度に含有する水溶液に対しても吸収倍率が低下せずに高い値を維持しており、単量体（Ａ）の効果がわかる。繊維２〜４は親水性単量体（Ｃ）及び架橋性単量体（Ｄ）としてＡＡとＨＥＡを併用し、可塑化単量体（Ｂ）として用いたＡＮの組成を変えた系であるが、ＡＮの組成が高くなるほど繊維物性は向上するが、吸収性能は低下する傾向にある。繊維５〜７は両イオン性ビニル系単量体（Ａ）であるＤＡＰＭＢの組成を変化させた系であり、ＤＡＰＭＢの組成の低下と共に電解質水溶液に対する吸収倍率が低下するが、本願発明の範囲を充たさない繊維７は電解質水溶液に対する吸収性能が大きく低下している。繊維８〜１０は親水性単量体（Ｃ）及び架橋性単量体（Ｄ）の組成を変化させた系であり、繊維物性はそれほど高くないが、純水及び電解質水溶液共に高い吸収性能を発揮している。繊維１１〜２０は可塑化重合体（ＩＩ）を添加した系であり、条件により異なるがいずれも高い繊維物性と良好な吸収性能を両立している。一方、比較例ではいずれも純水に対しては高い吸収性能を発揮するが、高濃度及び多価イオンを含有する電解質水溶液に対しては著しく吸収倍率が低下しており、本願発明の繊維の優位性が明確である。尚、両イオン性ビニル系単量体（Ａ）の中では、分子内に親水性の強いアミド結合を有するＤＡＰＭＢとＤＭＰＭＢの方がアミド結合を持たないＤＭＥＭＢよりも比較的高い吸収性能を示し、これらの単量体の優位性が認められる。
【００５７】
次に、いくつかの繊維について平衡吸湿率を測定した。乾燥した繊維を２０℃、６５％ＲＨの恒温恒湿器に入れ、４８時間後の重量増加分から下式に従って吸湿率を算出した。結果を表２に示す。
吸湿率（％）＝（吸湿重合体重量−絶乾重合体重量）÷絶乾重合体重量×１００
また、吸湿した状態での繊維の粘着性を触感により評価した。結果を表２に示す。尚、粘着性評価での各記号の意味は次の通りである。
○：粘着性小
△：粘着性中
×：粘着性大
−：評価せず
【００５８】
繊維１は４３％と高い吸湿率を示すが、ＡＮを共重合することにより吸湿率は２２％に低下し粘着性も低下した。さらに、繊維１２ではＰＶＡ−２１７を添加することにより、吸湿率は１６％と大きく低下すると共に粘着性も大きく減少し、非常に扱いやすい繊維となる。従って、これらの可塑化単量体（Ｂ）及び可塑化重合体（ＩＩ）を使用することの有効性が認められる。
【００５９】
【発明の効果】
本発明の高塩水吸収性繊維は、高い塩水吸収性能と共に繊維であるがゆえの加工性の高さを利用して、これまで使用することができなかったような分野、用途へ極めて有効に使用することができる。特に、海水、尿、血液、塩類土壌地下水等の電解質を高濃度で含有する水性媒体を吸収させる様な用途に絶大な効果を発揮するため、生活用品だけでなく、一般土木、各種資材用途にも有用である。例えば、紙おむつや生理用品等の吸収剤、止水パッド、血液用フローストッパー、農園芸用保水剤、生鮮食品用ドリップ吸収シート、塩類土壌改良剤、地中及び海中ケーブル用止水剤、鋼管矢板用止水剤等の用途が挙げられる。さらに、本発明の高塩水吸収性繊維は、繊維状であるために不織布、各種成形体、エレメント等に容易に成形加工することができるため、任意の形態に加工して種々の用途に容易に応用展開することができる。[0001]
[Industrial application fields]
The present invention relates to a high salt water-absorbing fiber comprising a vinyl polymer crosslinkable composition having amphoteric side chain groups. This fiber is useful for absorbing an aqueous solution containing an electrolyte such as seawater at a high concentration, and can be easily applied to various uses by utilizing its processability.
[0002]
[Prior art]
Water-absorbing resin that absorbs water several hundred times its own weight is used in absorbents such as paper diapers and sanitary products, water retention materials for agriculture and horticulture, soil conditioners, water-stopping agents, and the like. Examples of such water-absorbent resins include starch-acrylonitrile graft copolymer hydrolysates, starch-acrylic acid graft copolymers, carboxymethylcellulose cross-linked products, vinyl acetate-methyl acrylate copolymer hydrolysates, Acrylate cross-linked products are known.
[0003]
In general, water-absorbing resins are mainly supplied in powder form, but some are fibrous, and are made of non-woven fabrics, molded bodies (rods and disks), elements, taking advantage of their good workability. Agricultural and horticultural water retention agent, drip absorption sheet for fresh food, oil / water separation filter, hemostatic pad, blood flow stopper, anti-condensation sheet, fire-fighting / disaster prevention material, cable waterproofing agent, steel pipe Developed for various uses such as sheet pile waterproofing agent. As such a water-absorbing fiber, a fiber having a core-sheath two-layer structure in which an acrylonitrile-based fiber is an inner layer and a cross-linked polyacrylate is an outer layer in JP-A-54-138693 maintains good fiber properties. However, it is disclosed as exhibiting high water absorption. Japanese Laid-Open Patent Publication No. 6-65810 discloses a superabsorbent fiber made of a copolymer of a vinyl monomer having a carboxyl group and a vinyl monomer having a hydroxyl group and / or an amino group.
[0004]
However, these water-absorbing resins and water-absorbing fibers show very good absorbency with respect to pure water, ion-exchanged water or low-concentration electrolyte aqueous solution, but electrolytes such as seawater, salt water, blood, sweat, urine, etc. For an aqueous solution containing, there is a disadvantage that the absorption capacity is lowered. In particular, for high-concentration electrolyte aqueous solutions such as seawater or polyvalent metal salt aqueous solutions, the absorption performance is extremely lowered, and the application is limited.
[0005]
In order to enhance the absorption capacity for the aqueous electrolyte solution, for example, JP-A-61-36309 discloses a crosslinked polymer containing sulfoalkyl (meth) acrylate, and JP-A-62-266140 discloses a polyether. A cross-linked copolymer of a (meth) acrylate having a side chain and a monomer having a sulfonic acid group has been proposed as a salt-resistant water-absorbing agent. However, even with these water-absorbing resins, the absorption capacity is reduced with respect to a high concentration electrolyte aqueous solution or a polyvalent metal salt aqueous solution.
[0006]
As described above, such a highly water-absorbent resin is generally supplied in powder form, and if the resin can be directly formed into a fiber, the high workability can be utilized to make a nonwoven fabric, various molded articles, It becomes easy to develop into various applications by processing into elements. It is very difficult to impart easy moldability and good molded article physical properties while maintaining high absorbency in the water absorbent resin, and if the molded article physical properties are improved, a decrease in water absorption performance is inevitable. Moreover, such a highly water-absorbent resin has a very strong hygroscopic property, and has a drawback that when it absorbs moisture, the resin becomes sticky, making it difficult to handle the manufacturing process and processing.
[0007]
[Problems to be solved by the invention]
In order to overcome the problems as described above, the present inventor has reached the present invention as a result of intensive studies on a fibrous water-absorbing resin that is highly absorbent to an aqueous electrolyte solution. The development of fibers having excellent absorbency for aqueous electrolyte solutions, particularly high-concentration electrolyte aqueous solutions, and polyvalent metal salt aqueous solutions is a field where water-absorbing resins or water-absorbing fibers could not be used so far. Applications, especially for applications that absorb medium containing high concentrations of electrolytes such as seawater, are possible, and the increase in absorption capacity greatly increases the amount of fiber or resin required to absorb aqueous electrolyte solutions. Since it can be reduced, the user can save resources and save money. Furthermore, since it is fibrous, it can be processed directly into a non-woven fabric or element, and can be easily developed for various uses.
[0008]
[Means for Solving the Problems]
An object of the present invention is to provide a copolymer containing a zwitterionic vinyl monomer (A), preferably a vinyl monomer having a carboxybetaine type functional group, in the range of 10% by weight to 99% by weight. A fiber having excellent absorbability with respect to an aqueous electrolyte solution can be provided, which can be achieved by a high-salt water-absorbing fiber characterized by comprising a crosslinkable composition of the polymer (I). Here, the electrolyte refers to a substance that dissolves in water or another solvent and the solution conducts ion conduction, and the aqueous electrolyte solution refers to an aqueous solution in which one or more kinds of such substances are dissolved.
[0009]
The present invention is described in detail below. First, the amphoteric vinyl monomer (A) has both an anionic group and a cationic group in the same monomer unit, and one or more monomers are employed. An anionic group has the property of being ionized in an aqueous medium to become an anion. For example, there are a carboxyl group, a sulfonic acid group, and a phosphoric acid group. A cationic group is ionized in an aqueous medium to become a cation. For example, amino groups, secondary and tertiary amino groups, and quaternary ammonium groups can be exemplified.
[0010]
Such a monomer (A) includes the following chemical formula 2 (where R is ₁ Is a hydrogen atom or a methyl group, R ₂ Is a linear or branched alkylene or hydroxyalkylene group having 0 to 6 carbon atoms, R _Three And R _Four Each independently represents a methyl or ethyl group, R _Five Represents a linear or branched alkylene group or hydroxyalkylene group having 1 to 10 carbon atoms, X represents an ester group, an amide group, or a substituted or unsubstituted phenylene group. A vinyl monomer having a carboxybetaine type functional group represented by
[0011]
[Chemical formula 2]

[0012]
In Formula 2, X is an amide group, R _Three And R _Four Is a methyl group, R _Five By using a (meth) acrylamide-type carboxybetaine-type monomer in which Z is an alkylene group having 1 to 3 carbon atoms as the zwitterionic vinyl-based monomer (A), a highly electrolytic aqueous solution-absorbing fiber can be obtained. Can be obtained. That is, the hydrophilicity of the polymer increases due to the presence of a strongly hydrophilic amide bond introduced into the monomer side chain group, so that the absorption capacity is improved.
[0013]
In many cases, the carboxybetaine type monomer can be synthesized by a reaction between a corresponding tertiary amine type monomer and a monohaloalkylcarboxylic acid. For example, N, N-dimethyl-N- (2-methacryloyloxyethyl) -N- (carboxymethyl) ammonium inner salt can be synthesized by reacting dimethylaminoethyl methacrylate and sodium monochloroacetate in methanol. The amphoteric vinyl monomer (A) of the present invention can also be synthesized by a reaction between a tertiary amine monomer and a cyclic ester such as propiolactone. In addition, N, N-dimethyl-N- (2-methacryloyloxyethyl) -N- (carboxyethyl) ammonium inner salt, N, N-dimethyl-N- (2-acryloyloxyethyl) -N- (carboxymethyl) Carboxybetaine type monomers such as ammonium inner salt, N, N-dimethyl-N- (2-acryloyloxyethyl) -N- (carboxyethyl) ammonium inner salt are the zwitterionic vinyl monomers in the present invention ( A) can be preferably used.
[0014]
Further, as the zwitterionic vinyl monomer (A), N, N-dimethyl-N- (3-acrylamidopropyl) -N- (carboxymethyl) ammonium inner salt, N, N-dimethyl-N- (3 -Methacrylamidopropyl) -N- (carboxymethyl) ammonium inner salt, N, N-dimethyl-N- (3-acrylamidopropyl) -N- (carboxyethyl) ammonium inner salt, N, N-dimethyl-N- ( (Meth) acrylamide type carboxybetaine type monomers such as 3-methacrylamideamidopropyl) -N- (carboxyethyl) ammonium inner salt can be more suitably used in the present invention.
[0015]
The present invention also includes the case where zwitterionic functional groups are introduced into the polymer and the fiber by a polymer reaction with respect to the polymer and the fiber comprising the polymer. That is, a method of introducing a zwitterionic functional group by a polymer reaction between a polymer / fiber having a tertiary amino group and a monohaloalkylcarboxylic acid, or a reaction between a polymer / fiber and a compound having a zwitterionic functional group A fiber that is highly absorbable with respect to the aqueous electrolyte solution can also be obtained by adopting the method introduced by the above method, the method of graft polymerizing the zwitterionic vinyl monomer (A) to the polymer / fiber, and the like.
[0016]
By containing the zwitterionic vinyl monomer (A) in the copolymer (I) as a copolymerization component within the range of 10% by weight to 99% by weight, the aqueous electrolyte solution which is the subject of the present invention can be obtained. And highly absorbent fibers are obtained. If the amphoteric vinyl monomer (A) is less than 10% by weight, sufficient electrolyte aqueous solution absorbability cannot be obtained. Therefore, the amphoteric vinyl monomer (A) is at least 10% by weight, preferably 20% by weight. % Or more is desirable.
[0017]
In the present invention, a monomer other than the zwitterionic vinyl monomer (A) can be used in the copolymer (I) for the purpose of improving the fiber physical properties and the fiber absorption performance is hindered. There are no restrictions on the type within a range. That is, one or more kinds of radically polymerizable vinyl monomers can be appropriately selected and used for reasons such as improving physical properties such as strength of the polymer according to the purpose of use. In particular, it is desirable to use the plasticizing monomer (B) in order to impart plasticity, flexibility and toughness to the fiber.
[0018]
Examples of the plasticizing monomer (B) include acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate. Radical polymerizable monomers such as styrene can be preferably used.
[0019]
In particular, by using acrylonitrile as at least one component of the plasticizing monomer (B), good physical properties can be imparted to the fiber of the present invention. That is, by copolymerizing acrylonitrile, the copolymer (I) can be provided with flexibility, physical strength and low hygroscopicity, and the gel strength after water absorption can be improved.
[0020]
By containing at least one or more kinds of plasticizing monomers (B) as a copolymerization component in the range of 10 wt% to 40 wt% in the copolymer (I), the fiber physical properties are improved. However, the higher the composition of the plasticizing monomer (B) in the copolymer (I), the better the physical properties of the fiber. However, in order not to greatly reduce the water absorption performance of the fiber, it is 40% by weight or less, preferably 35% by weight. % Or less is desirable. Further, if the composition of the plasticizing monomer (B) is low, it is difficult to obtain sufficient fiber physical properties, so that it is desirable that the content is 10% by weight or more, preferably 20% by weight or more.
[0021]
In addition, the hydrophilic monomer (C) is contained in the copolymer (I) for reasons such as improving the fiber absorption performance, improving fiber properties, using as a crosslinking component, and reducing production costs. It is recommended that the absorption performance with respect to salt water is not extremely reduced. Such a hydrophilic monomer (C) has a hydrophilic functional group such as a carboxyl group, an amide group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, a quaternary ammonium group, or a polyethylene glycol group. A vinyl-type monomer is mentioned. Further, a monomer that can easily introduce a hydrophilic functional group by hydrolysis or the like can also be used.
[0022]
Examples of the monomer having such a hydrophilic functional group and that can be introduced include acrylic acid and its alkali salts, methacrylic acid and its alkali salts, itaconic acid, acrylonitrile, acrylic acid alkyl esters, methacrylic acid alkyl esters, Acrylamide, methacrylamide, N-substituted alkylacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylamide, vinyl acetate, vinyl sulfonic acid and its alkali salt, methallyl sulfonic acid and its alkali salt Styrene sulfonic acid and its salt, 2-acrylamido-2-methylpropane sulfonic acid and its alkali salt, 2-methacryloyloxyethane sulfone And alkali salts thereof, mono (2-acryloyloxyethyl) acid phosphate, mono (2-methacryloyloxyethyl) acid phosphate, 3-methacrylamidopropyldimethylamine and its salt, 2-methacryloyloxyethyldimethylamine and its salt, 2 -Methacryloyloxyethyl diethylamine and salts thereof, 3-methacrylamidopropyltrimethylammonium chloride, N-vinyl-2-pyrrolidone, polyethylene glycol methacrylate, polyethylene glycol acrylate, etc., and these monomers are used alone or in combination. Can be used.
[0023]
The composition of the hydrophilic monomer (C) in the copolymer (I) is 70% by weight or less, preferably in the range of 10% by weight to 50% by weight, in order to develop high absorbability with respect to the aqueous electrolyte solution. It is desirable.
[0024]
In order for the water-absorbing resin or water-absorbing fiber to absorb the aqueous medium and maintain the swollen state without dissolving in the medium, it is necessary to introduce a crosslinked structure into the polymer by covalent bond, electrostatic bond, hydrogen bond, etc. It is. In order to introduce a crosslinked structure to the copolymer (I) in the present invention, a polyfunctional radical polymerizable monomer such as a divinyl compound can be used as the crosslinkable monomer (D). It is practically impossible to form a fiber after polymerization, and it is necessary to perform the molding simultaneously with the polymerization. For example, a casting polymerization method is employed in which the monomer composition is cast into a capillary tube and then polymerized and fiberized in that state.
[0025]
Examples of the polyfunctional radical polymerizable monomer include bisacrylamides, di (meth) acrylic acid esters, diallyl compounds, and the like. Specifically, N, N-diallylmethacrylamide, diallylamine, N, N -Bisacrylamide acetic acid, N, N'-bisacrylamide acetic acid methyl ester, N, N'-methylenebisacrylamide, N, N-benzylidenebisacrylamide, diallyl succinate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, diethyl Glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 2 -Hydroxy-3-acryloyloxypropyl methacrylate, glycerin dimethacrylate, neopentyl glycol dimethacrylate, diallylacrylamide and the like can be used in the present invention.
[0026]
The composition in the copolymer (I) of such a polyfunctional radical polymerizable monomer is preferable because the polymer that has absorbed the aqueous medium does not dissolve in the medium and does not have fluidity or adhesiveness. Is preferably 0.01% by weight or more. Further, when the composition of the polyfunctional radically polymerizable monomer is increased, the absorption capacity is lowered, so that the composition is 1% by weight or less, preferably 0.1% by weight or less.
[0027]
As another method for introducing a crosslinked structure into a polymer, there is a crosslinking treatment of a monomer having a functional group capable of crosslinking after polymerization. That is, after the composition of the copolymer (I) is formed into a fiber, it is subjected to a crosslinking treatment to introduce a crosslinked structure. In the present invention, when a monomer capable of crosslinking treatment, that is, a monomer capable of introducing a crosslinked structure by post-treatment is employed as the crosslinking monomer (D), chemically with the monomer (D). A compound that binds to form a crosslinked structure may be used, and this compound is referred to as a crosslinking aid. In addition, when a monomer that self-crosslinks by heat treatment or the like is used, a crosslinking aid is not necessarily required.
[0028]
The crosslinkable monomer (D) may be the same monomer as the hydrophilic monomer (C). In that case, the crosslinkable monomer (D) is a hydrophilic monomer (C). The monomer component contributed to the cross-linked structure after the cross-linking treatment in FIG.
[0029]
Examples of the monomer capable of introducing such a crosslinked structure include a carboxyl group, an amide group, a nitrile group, a methylol group, a glycidyl group, a hydroxyl group, a monomer containing an imino group, and an acid anhydride monomer in the present invention. It can be preferably used. For example, acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacrylamide, acrylonitrile, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylamide, hydroxypropyl acrylate, hydroxypropyl methacrylate, Minol methacrylate etc. are mentioned.
[0030]
As the crosslinking aid, for example, when the crosslinkable monomer (D) has a carboxyl group, a functional group that can react with a carboxyl group such as a hydroxyl group, an epoxy group, an amino group, or a methylol group to form a chemical bond. Polyfunctional compounds having two or more, such as ethylene glycol, propylene glycol, glycerin, glycidyl alcohol, diglycidyl ether, glycerin triglycidyl ether, ethylene glycol diglycidyl ether, ethanolamine, ethylenediamine, propylenediamine, polyethylene glycol, polyvinyl Alcohol, trimethylol melamine, pentaerythritol, trimethylolpropane, polyethyleneimine, urea and the like can be mentioned. Another example is cross-linking with formaldehyde. Furthermore, a monomer having a functional group capable of forming a chemical bond with a carboxyl group can be used as a crosslinkable monomer (D) for crosslinking together with a monomer having a carboxyl group.
[0031]
In the case where the crosslinkable monomer (D) has a hydroxyl group, the crosslinking monomer (D) has a hydroxyl group such as a carboxyl group, an acid anhydride, an aldehyde group, or an isocyanate group, which has two or more functional groups capable of reacting with a hydroxyl group to form a chemical bond. Functional compounds such as malonic acid, succinic acid, glutaric acid, malic acid, propane-1,2,3-tricarboxylic acid and their anhydrides, glyoxal, glutaraldehyde, hexamethylene diisocyanate, cyclohexane diisocyanate, etc. As an agent. Furthermore, a monomer having a functional group capable of forming a chemical bond with a hydroxyl group can be used as a crosslinkable monomer (D) for crosslinking together with a monomer having a hydroxyl group.
[0032]
In the case where a hydroxyl group forms a crosslinked structure by hydroxyl groups or a hydrogen bond with a carboxyl group, it is not necessary to use a crosslinking aid. For example, if vinyl acetate or (meth) acrylic acid ester is used as the plasticizing monomer (B) and a hydroxyl group or a carboxyl group is generated by hydrolysis of the ester, the hydrogen-bonded microcrystalline structure is crosslinked by heat treatment. As a point, it is possible to absorb the aqueous medium and maintain the swollen state without particularly introducing a covalently crosslinked structure, and such a method for introducing a crosslinked structure can also be employed in the present invention.
[0033]
Cross-linking is also possible by carrying out cross-linking by forming an acid anhydride, cross-linking by an ester bond, or cross-linking by an ether bond by using a dehydration catalyst with a carboxyl group, a carboxyl group and a hydroxyl group, or hydroxyl groups. A structure can be introduced.
[0034]
When the crosslinkable monomer (D) has a nitrile group, a polyfunctional compound having two or more functional groups capable of reacting with a nitrile group such as an amino group to form a chemical bond, such as hydrazine, Ethylene diamine, propylene diamine, butylene diamine, pentamethylene diamine, hexamethylene diamine, both-terminal aminated polyethylene glycol and the like can be mentioned as crosslinking aids. Furthermore, a monomer having a functional group capable of forming a chemical bond with a nitrile group can be used as a crosslinkable monomer (D) together with a monomer having a nitrile group for crosslinking.
[0035]
A copolymer (I) is synthesized using one or more of these crosslinkable monomers (D) having postcrosslinkability, and after polymerization, formed into a fiber by an arbitrary method, and then crosslinked. The high-salt water-absorbing fiber of the present invention can be easily produced by the method of introducing a cross-linked structure. In addition, what is necessary is just to select suitably the crosslinking process in this invention according to the kind of used crosslinkable monomer (D), However, The method by dry heat processing is employ | adopted suitably.
[0036]
In particular, a monomer having a carboxyl group and a monomer having a hydroxyl group are used in combination as a crosslinkable monomer (D), and after the copolymer (I) composition is formed into a fiber, a crosslinked structure is introduced. This method is more preferably employed in the present invention because of the ease of crosslinking treatment and the wide range of processing conditions.
[0037]
The copolymer (I) of the present invention may be prepared using any conventional radical polymerization method. That is, any method of bulk polymerization, aqueous precipitation polymerization, suspension polymerization, reverse phase suspension polymerization, emulsion polymerization, and solution polymerization may be used, and depending on the purpose, the form of the polymer to be obtained is considered as appropriate. Just choose. However, in general, a polymerization system using water as a medium is desirable from the viewpoint of cost and environment. Examples of the method for generating radicals include a method using a radical polymerization catalyst, a method of irradiating radiation, an electron beam, and ultraviolet rays. Examples of the radical polymerization catalyst include peroxides such as hydrogen peroxide, benzoyl peroxide and cumene hydroperoxide, azo compounds such as azobisisobutyronitrile and azobiscyanovaleric acid, and persulfates such as ammonium persulfate and potassium persulfate. Examples thereof include radical generators such as salts, and redox initiators composed of combinations of these radical generators and reducing agents such as sodium bisulfite and L-ascorbic acid. Examples of the polymerization medium include water, an aqueous electrolyte solution, methanol, acetone, dimethylformamide, and the like, and may be appropriately selected depending on the polymerization method.
[0038]
In the present invention, the fiber strength and low adhesion at the time of moisture absorption are obtained by adding at least one plasticized polymer (II) selected from polyvinyl alcohol, polyethylene glycol and polyethylene oxide together with the copolymer (I) in the fiber. The fiber physical properties such as properties can be dramatically improved. In addition, a polymer having a large number of hydroxyl groups, such as polyvinyl alcohol, is obtained by combining a monomer having a functional group that reacts with a hydroxyl group to form a chemical bond in the copolymer (I). ), It is possible to form a cross-linked structure by a cross-linking treatment, so that the plasticized polymer (II) does not elute at the time of water absorption. The degree of polymerization and saponification of polyvinyl alcohol and the degree of polymerization of polyethylene glycol and polyethylene oxide may be appropriately selected according to the purpose in consideration of fiber properties, absorption performance, moldability into fibers, and the like. In particular, when polyvinyl alcohol is used as the plasticized polymer (II), the fiber strength is greatly improved, and the hygroscopicity is greatly reduced.
[0039]
The composition of the plasticized polymer (II) in the fiber is desirably 5% by weight or more in order to develop good fiber properties. Further, in order not to greatly reduce the fiber absorption performance, it is desirable that the composition is 20% by weight or less, preferably 15% by weight or less.
[0040]
The fiber production method in the present invention includes the above-described casting polymerization method and a normal spinning method. In the present invention, fiberization by a normal spinning method is more preferably employed. As the spinning method, any spinning method including a wet spinning method, a dry wet spinning method, and a dry spinning method using a solution of the copolymer (I) as a stock solution can be employed. In addition, as the fiber structure, a composite structure such as a core-sheath structure, a sea-island structure, a side-by-side structure, or the like can be suitably employed, and may be appropriately selected depending on the purpose. For example, if a core-sheath fiber having a crosslinkable composition of the copolymer (I) of the present invention in the core part is used as the core part, the fiber part has extremely excellent fiber properties as well as high absorbency. Fiber is obtained.
[0041]
In the wet spinning method and the dry and wet spinning method, the copolymer (I), the plasticized polymer (II) as necessary, and various additives as necessary are dissolved in an appropriate solvent and adjusted to an appropriate viscosity. The high salt water absorptive fiber of the present invention can be produced by preparing a stock solution, spinning from a porous nozzle in a poor solvent, and stretching as necessary, followed by crosslinking treatment. In this case, examples of the solvent include water, methanol, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and the like, and these can be used alone or in combination. Examples of the poor solvent include acetone, methyl ethyl ketone, toluene, ethyl acetate, hexane, and the like. These can be used alone or in combination or in combination with a solvent.
[0042]
In the dry spinning method, the copolymer (I), if necessary, the plasticized polymer (II) and various additives as necessary are dissolved in an appropriate solvent, adjusted to an appropriate viscosity to obtain a stock solution, and heated atmosphere. The high-salt water-absorbing fiber of the present invention can be produced by spinning in, evaporating the solvent, performing a stretching operation as necessary, and then crosslinking. Examples of the solvent include water, methanol, dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like, and these can be used alone or in combination. In the present invention, fiber formation by a dry spinning method using water as a solvent is particularly preferable from the viewpoints of cost, safety, working environment and the like.
[0043]
Hereinafter, a method for producing the high salt water-absorbing fiber of the present invention using the dry spinning method will be described. The spinning stock solution is preferably a polymerization system using water as a solvent, and the solution after polymerization becomes the stock solution as it is. It is necessary to adjust the concentration of the copolymer (I) and the plasticized polymer (II) added as necessary in the stock solution so as to obtain a viscosity suitable for spinning. % To 50% by weight, preferably 18% to 25% by weight. The viscosity of the stock solution is not particularly limited as long as the elongational viscosity in a heated atmosphere is sufficient and stable spinning without breaking the yarn is possible, but generally the viscosity with a B-type viscometer at 25 ° C. It is in the range of 100 poise to 4000 poise.
[0044]
The spinning temperature of the stock solution is generally in the range of 30 ° C to 80 ° C. The temperature of the heating atmosphere may be appropriately selected according to the solvent to be used, but it is generally set to 100 ° C to 300 ° C, preferably 150 ° C to 250 ° C. In addition, when extending | stretching a fiber after a drying process, a extending | stretching process can be performed smoothly by setting the solvent fraction of the fiber when it comes out of a heating atmosphere to about 10 weight%-15 weight%. The fiber draw ratio may be appropriately set so as to impart good fiber properties, but is generally about 1.5 to 10 times.
[0045]
As the crosslinking treatment for imparting a crosslinked structure to the fiber, a dry heat treatment method is suitably employed in the present invention. That is, as the crosslinkable monomer (D) in the copolymer (I), one or more monomers that form a crosslinked structure by heat treatment are employed. At this time, it is desirable that the plasticized polymer (II) also simultaneously forms a crosslinked structure. The temperature of the dry heat treatment may be set so that crosslinking can be performed in a desired time, but is generally in the range of 150 ° C to 300 ° C. The fiber absorption performance can be controlled by changing the crosslinking treatment conditions (temperature, time), and the conditions may be set as appropriate according to the desired performance. However, when the cross-linked structure is too small, it is necessary to be careful because the elution of the polymer from the absorbed fiber increases.
[0046]
The final fiber diameter is generally about 5 to 100 μm, preferably about 15 to 50 μm. The raw fiber cotton is provided in the form of continuous filaments or staples cut to an appropriate length, and is processed and used as needed from yarns, non-woven fabrics, various molded products, elements, and the like.
[0047]
[Action]
The reason why the high-salt water-absorbing fiber of the present invention is highly absorbent with respect to the aqueous electrolyte solution has not yet been fully elucidated, but the following can be said. That is, a homopolymer of a linear carboxybetaine monomer that is not cross-linked exhibits good solubility not only in pure water but also in an aqueous electrolyte solution, and further contains a high concentration aqueous electrolyte solution and an aqueous electrolyte solution containing polyvalent ions. The polymer having a crosslinked structure also swells with respect to the aqueous electrolyte solution and exhibits high absorbability. Therefore, the fiber containing such a polymer also shows high absorbency with respect to the electrolyte aqueous solution.
[0048]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated concretely according to an Example, the scope of the present invention is not limited only to these Examples.
[0049]
Example 1
In this example, as the zwitterionic vinyl monomer (A), N, N-dimethyl-N- (3-acrylamidopropyl) -N- (carboxymethyl) ammonium inner salt (hereinafter abbreviated as DAPMB) is used. Obtained from Jin Corporation. N, N-dimethyl- (3-methacrylamideamidopropyl) -N- (carboxymethyl) ammonium inner salt (DMPMB), N, N-dimethyl-N- (2-methacryloyloxyethyl) -N- (carboxymethyl) ) Ammonium internal salt (DMEMB) was synthesized by reacting the corresponding tertiary amine monomer of each monomer with sodium monochloroacetate in methanol at 60 ° C.
[0050]
Acrylonitrile (AN) and methyl acrylate (MA) were used as the plasticizing monomer (B). As the hydrophilic monomer (C), acrylic acid (AA) and hydroxyethyl acrylate (HEA) were used. Moreover, AA and HEA which are monomers (C) were used together as the crosslinkable monomer (D) having postcrosslinkability. N-methylolacrylamide (NMAM) is also a hydrophilic monomer (C), but was also used as a crosslinkable monomer (D). All AA was used for the polymerization after neutralizing about 70 mol% of the addition amount with an aqueous NaOH solution. As the plasticized polymer (II), polyvinyl alcohol (PVA-217 (average polymerization degree: 1700, saponification degree: 88%) and PVA-205 (polymerization degree: 500, saponification degree: 88%), Kuraray Co., Ltd. And polyethylene glycol (PEG-6000 and PEG-20000, manufactured by Wako Pure Chemical Industries, Ltd.) were used.
[0051]
Copolymer (I) is prepared by dissolving or suspending a predetermined amount of various monomers in distilled water and adding 0.8% by weight of potassium persulfate (KPS) as an initiator to the total monomer weight. , And polymerized at 70 ° C. with stirring for 5 hours. When a redox system consisting of KPS and sodium bisulfite (SHS) was used as an initiator, polymerization was performed at 60 ° C. with stirring for 5 hours. At this time, KPS was used in an amount of 0.8% by weight based on the total monomer weight, and SHS was added in 1.2 mole equivalents to KPS in several portions. Similarly, the system to which the plasticized polymer (II) was added was polymerized by adding a predetermined amount of the plasticized polymer (II). The polymerized solution was degassed under reduced pressure and used as it was as a stock solution. The solid content of the stock solution was obtained by drying about 1 g of the stock solution at 120 ° C. for 4 hours and measuring the weight of the dried product. The viscosity of the stock solution was measured at 25 ° C. using a bismetholone viscometer (manufactured by Shibaura System Co., Ltd.). For comparison, a copolymer not containing the zwitterionic vinyl monomer (A) was also polymerized in the same manner as a stock solution. Table 1 shows the monomer charge composition of the stock solution polymerized in various compositions, the added amount of the plasticized polymer (II), the solid content of the stock solution, and the stock solution viscosity.
[0052]
[Table 1]

[0053]
Dry spinning was performed according to a conventional method. The stock solution was spun from a perforated nozzle into a heated atmosphere at about 200 ° C., stretched about twice and wound up. Then, dry heat treatment was performed under tension at 200 ° C. for 1 to 5 minutes to obtain dry fibers. The dry heat treatment time was set so that the fiber did not dissolve after absorbing the aqueous medium. The obtained fiber was cut into about 100 mm and subjected to the following various evaluations.
[0054]
The tensile strength and elongation of the fiber were measured according to the method described in JIS L 1015. The fiber denier was calculated from the fiber weight and fiber length. The absorption performance of the fibers was evaluated by measuring the absorption ratio with respect to pure water and various aqueous electrolyte solutions by the following method. 1 g of dried fiber was immersed in 500 ml of pure water and various electrolyte aqueous solutions for 2 hours, filtered through a 200 mesh wire mesh, drained for 10 minutes, and then the weight of the swollen fiber that absorbed the aqueous medium on the wire mesh was measured. The absorption capacity was defined as the number of grams of the aqueous medium absorbed per gram. As the electrolyte aqueous solution, 0.9 wt% NaCl aqueous solution, 10 wt% NaCl aqueous solution, 5 wt% CaCl ₂ An aqueous solution and artificial seawater (Aquamarine S, manufactured by Hachishu Pharmaceutical Co., Ltd.) were used. For comparison, commercially available superabsorbent fibers (Lanseal F, manufactured by Toyobo Co., Ltd.) were also evaluated in the same manner. Table 2 shows the strength of each fiber and the absorption capacity for various aqueous media.
[0055]
[Table 2]

[0056]
Fiber 1 is a fiber made of a copolymer of DAPMB, which is an amphoteric vinyl monomer (A), and NMAM, which is a crosslinkable monomer (D), and has low fiber properties but its absorption capacity is pure. Both water and various electrolyte aqueous solutions were high and very excellent. In particular, the absorption ratio is maintained at a high value without reducing the concentration of an aqueous electrolyte solution and an aqueous solution containing a high concentration of multivalent ions, and the effect of the monomer (A) can be seen. The fibers 2 to 4 are systems in which AA and HEA are used in combination as the hydrophilic monomer (C) and the crosslinkable monomer (D), and the composition of AN used as the plasticizing monomer (B) is changed. However, the higher the AN composition, the better the fiber properties, but the absorption performance tends to decrease. Fibers 5 to 7 are systems in which the composition of DAPMB, which is the zwitterionic vinyl monomer (A), is changed, and the absorption capacity with respect to the aqueous electrolyte solution decreases with a decrease in the composition of DAPMB. The unfilled fiber 7 has a greatly reduced absorption performance with respect to the aqueous electrolyte solution. The fibers 8 to 10 are systems in which the composition of the hydrophilic monomer (C) and the crosslinkable monomer (D) is changed, and the fiber properties are not so high, but both the pure water and the aqueous electrolyte solution have high absorption performance. Demonstrating. The fibers 11 to 20 are systems to which a plasticized polymer (II) is added, and both have high fiber properties and good absorption performance, although they differ depending on the conditions. On the other hand, all comparative examples exhibit high absorption performance with respect to pure water, but the absorption ratio is significantly reduced with respect to an aqueous electrolyte solution containing a high concentration and multivalent ions. The advantage is clear. Among amphoteric vinyl monomers (A), DAPMB and DPMMB having a strong hydrophilic amide bond in the molecule exhibit relatively higher absorption performance than DMEMB having no amide bond, The superiority of these monomers is recognized.
[0057]
Next, the equilibrium moisture absorption rate was measured for several fibers. The dried fiber was put into a constant temperature and humidity chamber at 20 ° C. and 65% RH, and the moisture absorption rate was calculated according to the following formula from the weight increase after 48 hours. The results are shown in Table 2.
Moisture absorption rate (%) = (hygroscopic polymer weight−absolute dry polymer weight) ÷ absolute dry polymer weight × 100
Moreover, the adhesiveness of the fiber in the moisture absorption state was evaluated by tactile sensation. The results are shown in Table 2. In addition, the meaning of each symbol in adhesive evaluation is as follows.
○: Low tackiness
Δ: Adhesive
×: High adhesiveness
-: Not evaluated
[0058]
The fiber 1 showed a high moisture absorption rate of 43%, but by copolymerizing AN, the moisture absorption rate was reduced to 22% and the tackiness was also reduced. Furthermore, in the fiber 12, by adding PVA-217, the moisture absorption rate is greatly reduced to 16% and the adhesiveness is greatly reduced, so that the fiber becomes very easy to handle. Therefore, the effectiveness of using these plasticized monomers (B) and plasticized polymer (II) is recognized.
[0059]
【The invention's effect】
The high-salt water-absorbing fiber of the present invention is extremely effectively used in fields and applications that could not be used so far, utilizing the high salt-water absorption performance and high processability due to the fiber. can do. In particular, not only for daily necessities, but also for general civil engineering and various materials, because it is extremely effective in applications that absorb aqueous media containing high concentrations of electrolytes such as seawater, urine, blood, and saline soil groundwater. Is also useful. For example, absorbents such as paper diapers and sanitary products, water stop pads, blood flow stoppers, agricultural and horticultural water retention agents, fresh food drip absorption sheets, salt soil amendments, underground and underwater cable water stop agents, steel pipe sheet piles Uses such as water-stopping agents are listed. Furthermore, since the high-salt water-absorbing fiber of the present invention is fibrous, it can be easily molded into a nonwoven fabric, various molded articles, elements, etc., so it can be processed into any form and easily used in various applications. Can be applied.

Claims (9)

Embedded image wherein R 1 is a hydrogen atom or a methyl group, R 2 is a linear or branched alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group, R 3 and R 4 are each independently a methyl group or An ethyl group, R 5 is a linear or branched alkylene group or hydroxyalkylene group having 1 to 10 carbon atoms, and X is an ester group, an amide group, or a substituted or unsubstituted phenylene group. Containing a zwitterionic vinyl monomer (A) selected from vinyl monomers having a betaine type functional group as a copolymerization component within a range of 10 wt% to 99 wt% , or having a crosslink A high-salt water-absorbing fiber, comprising a copolymer (I) which is post-crosslinkable .

The amphoteric vinyl monomer (A) is selected from (meth) acrylamide type monomers in which X in Formula 1 is an amide group, R3 and R4 are methyl groups, and R5 is an alkylene group having 1 to 3 carbon atoms. The high salt water absorptive fiber according to claim 1, wherein The copolymer (I) contains at least one plasticizing monomer (B) as a copolymerization component in the range of 10 wt% to 40 wt%. The high salt water absorptive fiber in any one. The high salt water absorptive fiber according to any one of claims 1 to 3, wherein acrylonitrile is used as at least one component of the plasticizing monomer (B). The copolymer (I) contains at least one hydrophilic monomer (C) as a copolymerization component in the range of 0% by weight to 70% by weight. The high salt water absorptive fiber in any one. Before the copolymer (I) is formed into a fiber, it is basically a linear polymer. After the forming, the crosslinkable monomer (D) having post-crosslinkability is subjected to a crosslinking treatment to be crosslinked. The high salt water absorptive fiber according to any one of claims 1 to 5, wherein the fiber is produced by introducing a structure. A cross-linking structure is obtained by using a vinyl monomer having a carboxyl group and a vinyl monomer having a hydroxyl group in combination as a cross-linkable monomer (D) having post-crosslinkability, and bonding a part of both monomers. The high-salt water-absorbing fiber according to any one of claims 1 to 6, wherein The high salt water absorptive fiber according to any one of claims 1 to 7, wherein the plasticized polymer (II) is contained in the fiber in a range of 5 wt% to 20 wt%. The high salt water absorptive fiber according to any one of claims 1 to 8, wherein polyvinyl alcohol is contained as the plasticized polymer (II).