JP3674202B2 - Antibacterial acrylonitrile fiber and method for producing the same - Google Patents

Description

【０００９】
また、上述した抗菌性アクリロニトリル系繊維を得る方法として、３０〜８０ｍｍｏｌ／Ｋｇのスルホン酸基を有するカチオン可染ＡＮ系繊維の製造工程中一次緻密化工程の後、下記一般式〔Ｖ〕で示される第４級アンモニウム塩系薬剤の１種以上を接触せしめ、その後スチ−ム弛緩熱処理することを特徴とする手段によりマラカイトグリ−ン飽和染着量が１．１％ｏｗｆ以上である抗菌性アクリロニトリル系繊維の製造方法が提供される。
【００１０】
【化５】

【００１１】
また、上述の抗菌性を兼備したカチオン可染ＡＮ系繊維を含有する繊維製品を得る方法として、３０〜８０ｍｍｏｌ／Ｋｇのスルホン酸基を有するカチオン可染ＡＮ系繊維を含有する繊維製品に、下記一般式〔VI〕で示される第４級アンモニウム塩系薬剤の１種以上を浸漬法又はパッドスチ−ム法により、９０℃以上の温度で吸着処理することを特徴とする手段によりマラカイトグリ−ン飽和染着量が１．１％ｏｗｆ以上である抗菌性アクリロニトリル系繊維を含有する繊維製品の製造方法が提供される。
【００１２】
【化６】

【００１３】
【発明の実施の形態】
以下本発明を詳述する。ここにおいて、３０〜８０ｍｍｏｌ／Ｋｇのスルホン酸基を有するカチオン可染ＡＮ系繊維とは、アクリロニトリル６０重量％以上、さらに好ましくは８０重量％以上とアクリロニトリルと共重合し得る他のビニル系単量体１種以上、ならびに必要に応じて所望量のスルホン酸基含有単量体とからなるアクリロニトリル系共重合体から形成されるカチオン可染ＡＮ系繊維を示称するものである。なおカチオン可染あるいはカチオン染料可染とは、アクリル繊維を構成する重合体分子中にアニオン性基を有しており、水溶液中でカチオン染料（解離してカチオンを生じる）とイオン結合することができる性質をいう。
【００１４】
アクリロニトリルと共重合し得るビニル系単量体としては、例えば酢酸ビニル等のビニルエステル類；塩化ビニル、臭化ビニル、塩化ビニリデン等のハロゲン化ビニル又はビニリデン類；アクリル酸メチル、メタアクリル酸メチル等の（メタ）アクリル酸低級アルキルエステル類（以下（メタ）アクリルの記載はアクリル酸とメタアクリル酸の両方を表現するものとする）；アクリルアミド，スチレン等を挙げることができる。
【００１５】
一般にアクリロニトリル系繊維のスルホン酸基の一部は、アクリロニトリルを重合させる時に使うレドックス触媒、例えば還元剤の酸性亜硫酸塩等が高分子鎖の末端にスルホン酸基として結合したものをもって充てることができる。
【００１６】
ここでいう所望量のスルホン酸基含有単量体とは、３０〜８０ｍｍｏｌ／Ｋｇのスルホン酸基を有するアクリロニトリル系共重合体を合成するため、上述の触媒から導入したスルホン酸基だけでは不足する場合に、これを補うために必要量のスルホン酸基含有単量体をアクリロニトリルと共重合させるときの該単量体の量をいう。また、レドックス触媒を使用しない場合には、３０〜８０ｍｍｏｌ／Ｋｇのスルホン酸基は，すべてスルホン酸基含有単量体から導入することが必要である。
【００１７】
係るスルホン酸基含有単量体としては、アクリロニトリルと共重合する事ができる限り特に限定されないが、メタアリルスルホン酸ソ−ダ、２−アクリルアミド−２−メチルプロパンスルホン酸、パラスチレンスルホン酸ソ−ダ、ビニルスルホン酸ソ−ダ等を挙げることができる。
【００１８】
出発繊維のカチオン可染アクリロニトリル系繊維は、スルホン酸基３０〜８０ｍｍｏｌ／Ｋｇ、好ましくは４０〜６０ｍｍｏｌ／Ｋｇを有することが必要である。３０ｍｍｏｌ／Ｋｇ未満では本発明の目的とする染色および洗濯によって低下しない抗菌性能と良好な濃染性が得られないためである。一方、８０ｍｍｏｌ／Ｋｇを越える場合には、本発明で使用する第４級アンモニウム塩系薬剤の吸着速度が速すぎ、均一な処理ができない不都合がある。また原綿の着色が増大（白度の低下）する問題が生じる。
【００１９】
本発明の抗菌性アクリロニトリル系繊維のマラカイトグリ−ン飽和染着量は、１．１％ｏｗｆ以上、好ましくは１．３％ｏｗｆ以上必要である。１．１％ｏｗｆに満たない場合には本発明の目的である黒、紺、エンジ、緋赤等の濃色染色が困難となり、また染色堅牢度特に湿潤堅牢度に問題が生じる。
【００２０】
なお、本発明でいうマラカイトグリ−ン飽和染着量とは、下記の条件で染色を行い、常法に従い残液比色法で吸光度を測定して、数１により染着度を求め、数２によりマラカイトグリーン飽和染着量（重量％対繊維重量、％ｏｗｆ）として求めたものを言う。
染液 ：保土谷化学（株）製 マラカイトグリ−ン ３．５％ｏｗｆ
ｐＨ調整剤：酢酸 １．５％ｏｗｆ
浴比 ：１／１００
温度 ：１００℃
時間 ：１５０分
測定法 ：日立製作所（株）製Ｕ−２０００型を用いて、６２０ｎｍの光に対する吸光度を測定する。
なお、本法で求める染着度が７０％を越える場合には、染液中のマラカイトグリ−ンを５．０％ｏｗｆにして再測定したものを言う。
【００２１】
【数１】

【００２２】
【数２】

【００２３】
本発明に係る第４級アンモニウム塩系薬剤としては、一般式〔Ｉ〕〜〔ＶＩ〕の何れも、Ｒ１の炭素数は８〜２１が好ましく、８未満では抗菌性能が低下する。また、Ｒ１の炭素数が２１を越えると抗菌性能の低下に加え、染色性が大幅に低下する。Ｒ２の炭素数は２〜５が好ましく、５を越えると染色性が低下する。さらに、Ｒ３、Ｒ４、Ｒ５の炭素数は１〜５が好ましく、５を越えると染色性が低下する。
【００２４】
本発明に係る第４級アンモニウム塩系薬剤として、好ましくは、ステアリル・アミド・プロピル・ジメチル・ヒドロキシエチル・アンモニウムナイトレ−ト、セチル・アミド・プロピル・ジメチル・ヒドロキシエチル・アンモニウムナイトレ−ト、ステアリル・アミド・プロピル・ジメチル・ヒドロキシエチル・アンモニウムクロライド、セチル・アミド・プロピル・ジメチル・ヒドロキシエチル・アンモニウムクロライド、ステアリル・アミド・プロピル・ジメチル・ヒドロキシエチル・アンモニウムブロマイド、ステアリル・アミド・エチル・ジエチル・ヒドロキシエチル・アンモニウムアセテ−ト、ステアリル・アミド・エチル・ジエチル・ヒドロキシエチル・アンモニウムホスフェ−ト、ステアリル・アミド・プロピル・ジメチル・エチル・アンモニウムエチルサルフェ−ト、セチル・アミド・プロピル・ジメチル・エチル・アンモニウムエチルサルフェ−ト、ステアリル・アミド・プロピル・ジエチル・メチル・アンモニウムメチルサルフェ−ト、セチル・アミド・プロピル・ジエチル・メチル・アンモニウムメチルサルフェ−ト、ステアリル・アミド・プロピル・トリメチル・アンモニウムメチルサルフェ−ト、セチル・アミド・エチル・ジエチル・メチル・アンモニウムメチルサルフェ−ト、ステアリル・アミド・エチル・トリメチル・アンモニウムメチルサルフェ−ト等を例示することができる。また、該薬剤のアクリロニトリル系繊維への吸着量（付与量）は、０．２〜３．０％ｏｗｆで、好ましくは０．７〜２．０％ｏｗｆであり、上記した薬剤の１種とすることも数種の薬剤を混用することもある。
【００２５】
次に、本発明の抗菌性アクリロニトリル系繊維の製造方法について述べる。該繊維は３０〜８０ｍｍｏｌ／Ｋｇのスルホン酸基を有するカチオン染料可染性アクリロニトリル系繊維の製造工程中の薬剤処理によって製造される。薬剤処理を施す工程は一次緻密化工程の後である。
３０〜８０ｍｍｏｌ／Ｋｇのスルホン酸基を有するカチオン可染ＡＮ系繊維の製造工程中一次緻密化工程の後とは、紡糸・延伸・水洗後に行われる乾燥緻密化工程の後を意味する。
一次緻密化工程とは、延伸されたトウまたはフィラメントには、繊維中のボイドに由来するある程度（２０〜８０重量％）の水分が残っているのであるが、この水分を除き水分が抜けた穴をつぶし、繊維を緻密化する工程をいう。
これには、トンネル乾燥機またはドラム乾燥機を使用し、高温低調湿状態で徐々に水分を取り除く方法と、ロ−ラ−乾燥機で高温乾熱且つある程度の緊張条件下で、急激に焼きつぶす方法等がある。
薬剤処理を紡糸以降、一次緻密化工程より前に行うと、繊維構造にはまだ無数の穴が存在しているため、薬剤が繊維内部に固定されにくく、乾燥緻密化までの各工程で脱落し、工程汚染・排水異常等を惹起する問題がある。
また、一次緻密化工程直前に薬剤処理すると高温で行う該工程で、繊維が着色しやすく、原綿白度の点で好ましくない。
【００２６】
また本発明に記載の第４級アンモニウム塩系薬剤の１種以上を接触せしめとは、本発明のアクリロニトリル系繊維の製造工程中一次緻密化工程の後のトウまたはフィラメントを本発明の第４級アンモニウム塩系薬剤に接触させることであり、その手段に制限はなくディップ→ニップ、スプレ−等いかなる方法でもよい。クリンパ−予熱槽等を利用した一例としての処方を示せば次の様である。すなわち、本発明の特定薬剤を該処理槽液中に、トウまたはフィラメントに対して吸着せしめる目標量を添加し、次にクリンパ−等を利用して一定に絞ることにより、トウまたはフィラメントに該薬剤を目標量付与（吸着）し、その後、キヤ−等を使用してスチ−ム弛緩熱処理することにより吸着を完成させる。
【００２７】
また本発明に記載のスチ−ム弛緩熱処理とは、キヤ−またはオ−トクレ−ブを使用して、本発明のトウをスチ−ム中でリラックスさせることをいう。また連続的にスチ−ムリラックスさせてもよい。
スチ−ムとしては、飽和水蒸気，過熱水蒸気等制限はないが、飽和水蒸気中で１０５℃〜１４０℃で処理することが望ましい。リラックスさせる程度としては５〜３０％が好ましい。
【００２８】
本発明に係る３０〜８０ｍｍｏｌ／Ｋｇのスルホン酸基を有するカチオン可染ＡＮ系繊維を含有する繊維製品とは、原綿（トウ，バラ毛等）、糸（綛，チ−ズ等）、編織物、毛布・ボア類、不織布等が挙げられ、その形態に限定はない。
【００２９】
また、本発明でいう浸漬法により処理するとは、本発明が対象とする繊維製品を所定量の薬剤を含有する処理浴中に浸漬して所定温度で処理することをいい、好ましくは、オ−バ−マイヤ−染色機等を使用して、通常の染色と同様なやり方で実施する方法が挙げられる。
オ−バ−マイヤ−染色機を使用した一例としての処方を示せば次のようである。すなわち、原綿（トウ，バラ毛）等をキャリヤ−に通常染色の場合と同様の方法で詰め込み、本発明の特定薬剤を槽液中に原綿等に対して吸着せしめる目標量を添加し、次ぎに昇温〜９０℃処理または昇温〜ボイル処理あるいは必要により高温高圧処理することにより吸着を完成させる。
【００３０】
またパッドスチ−ム法により処理するとは、本発明が対象とする繊維製品を所定量の特定薬剤を含有する処理液に含浸した後マングルで絞り、または遠心脱水して、さらにはまたスプレ−のみで所定量の薬剤を付与し、次いでスチ−ム処理することを言う。
例えば、本発明のカチオン可染ＡＮ系繊維単独又は該繊維を混紡してなるシ−ツ・毛布・ボアの生織等に対して、本発明の特定薬剤を吸着せしめる目標量を含浸・マングル絞り（ピックアップ量）で付与し、その後９０℃以上の温度でスチ−ム処理することにより吸着を完成させる。
【００３１】
【作用】
本願に係る抗菌性アクリロニトリル系繊維は、３０〜８０ｍｍｏｌ／Ｋｇのスルホン酸基を有する特定のカチオン可染ＡＮ系繊維に対して、抗菌性が大きく且つ染色性の低下が少ない特定構造の第４級アンモニウム塩系薬剤を該繊維の製造工程中一次緻密化工程の後接触せしめ、その後スチ−ム弛緩熱処理するか、あるいは浸漬法またはパッドスチ−ム法により、アクリロニトリル系繊維の二次転位温度以上の９０℃以上の温度で吸着せしめることで該特定抗菌薬剤が該繊維中に固定（スルホン酸基と結合）または保持（スルホン酸基とゆるい結合またはスルホン酸基の周辺に存在）されると考えられる。
そして、本抗菌性アクリロニトリル系繊維はマラカイトグリ−ン飽和染着量が１．１％ｏｗｆ以上であり、良好なカチオン染料染色性、すなわち濃染性を有し、また抗菌薬剤が繊維内部まで浸透、拡散しているため、一般的な繊維表面への付着または固着と異なり、染色及び繰り返し洗濯による抗菌性能の低下がなく、さらにはまた、各種製品への加工工程において、光、熱、加工薬剤等による変色、着色が少なくなるものと推察している。
また抗菌薬剤として、金属イオン（銀イオン、銅イオン）を採用していないことも前述の変色、着色が少ない理由と推察している。
また本発明者らは、抗菌性が大きく且つ染色性の低下が少ない抗菌薬剤として、本発明の様な第４級アンモニウム塩の分子中にアミド基を含む基本構造の化合物がよいことを見い出している。
【００３２】
【実施例】
以下に本発明の理解を容易にするため実施例を示すが、これらはあくまで例示的なものであり、本発明の要旨はこれらにより限定されるものではない。
なお、実施例中の部および百分率は特に断りのない限り重量基準で示す。なお、実施例において記述する抗菌性能、原綿白度および洗濯条件は、以下の方法により実施した。
【００３３】
（１）抗菌性能
試験菌株：黄色葡萄状球菌 Stapylococcus aureus ATCC 6538P
試験方法：繊維製品衛生加工協議会（ＳＥＫ）で定める方法により、滅菌試料布に試験菌のブイヨン懸濁液を注加し、密閉容器中で、３７℃、１８時間培養後の生菌数を計測し、植菌数Ａに対する標準布の菌数Ｂと試料の菌数Ｃの増減値差で求める。一般に増減値差が１．６以上あれば抗菌性能があると見なされるが、３．０以上が好ましい。
増減値＝ｌｏｇＣ−ｌｏｇＡ
増減値差＝（ｌｏｇＢ−ｌｏｇＡ）−（ｌｏｇＣ−ｌｏｇＡ）
【００３４】
（２）原綿白度
スガ試験機（株）製ＭＳＣ−５Ｎを使用し、Ｃ光源、２度視野条件下でサンプルを測色し、ＸＹＺ値を出し、ＪＩＳ−１０１５のＪｕｄｄ式によりＷ値（％）を求めた。なお、Ｗ値（％）は１００％に近い方が白い。
【００３５】
（３）洗濯条件
ＪＩＳ−Ｌ−０２１３の１０３法（家庭用洗濯機用）に従い、洗剤として第一工業製薬（株）製モノゲンユニを使用して洗濯を繰り返す。（１０回、２０回）
【００３６】
実施例１
常法に従ってアクリロニトリル９１％、アクリル酸メチルエステル９〜７％、メタアリルスルホン酸ソ−ダ０〜２％と変化させ、スルホン酸基量の異なるアクリロニトリル系重合体を合成し、濃度４６％のロダンソ−ダ水溶液に溶解し、重合体濃度が１２％である紡糸原液を作成した。
該原液を１０％、−３℃のロダンソ−ダ水溶液中に公知である３ｄ用口金を用いて押し出し、次いで冷延伸・熱延伸・水洗・乾燥緻密化工程の後、クリンパ−予熱槽を使用して、７０℃で各種第４級アンモニウム塩系薬剤を走行トウ重量に対して、純分で１．５％ｏｗｆ添加し、次にクリンパ−を利用して絞り、槽液濃度が平衡になった所で、クリンパ−後のトウを採取し、その後キヤ−で１２７℃×７分間スチ−ム弛緩熱処理を実施した。常法により油剤・乾燥・バリカットして試料Ｎｏ．１〜１２を得た。各試料のスルホン酸基量および使用した第４級アンモニウム塩系薬剤と、抗菌原綿としての諸特性の評価や、抗菌原綿３０％／日本エクスラン工業（株）製のＫ８−３ｄ７０％混糸を使用した天竺編地についての各種評価を行い、表１、表２、表３、表４に併記する。
【００３７】
【表１】

【００３８】
【表２】

【００３９】
【表３】

【００４０】
【表４】

【００４１】
表１、表２の本発明例の試料Ｎｏ．１，２，３，４，５は、出発繊維のスルホン酸基量が、本発明の３０〜８０ｍｍｏｌ／Ｋｇの範囲で、且つ本発明の特定第４級アンモニウム塩系薬剤を使用し試作され、また、マラカイトグリ−ン飽和染着量も本発明の１．１％ｏｗｆ以上あるため、濃染性・原綿白度・耐熱性何れも良好で、染色および繰り返し洗濯による抗菌性能の低下もないことが判る。
一方、表３、表４の比較例の試料Ｎｏ．６は、出発繊維のスルホン酸基量が少ないため、濃染性が劣り黒染不可で湿潤堅牢度も悪い。また抗菌性能の染色・洗濯耐久性が劣ることが判る。
また、表３、表４の比較例の試料Ｎｏ．７は、出発繊維のスルホン酸基量が非常に多く、抗菌薬剤の付着ムラが推定される。また原綿白度・耐久性も著しく劣ることが判る。
さらにはまた、表３、表４の比較例の試料Ｎｏ．８，９，１０，１１，１２は、第４級アンモニウム塩系薬剤を使用しているものの、本発明の特定構造外のため、濃染性および／または抗菌性能に関して問題があることが判る。
また、染色品の耐光性は、抗菌薬剤として第４級アンモニウム塩を使用し、繊維表面固着でなく、繊維内部へ浸透・拡散させているため、全般に良好であるが、中でも表２の本発明例の試料Ｎｏ．１，２，３，４，５は特に良好であった。
【００４２】
実施例２
実施例１の試料Ｎｏ．２と同じ組成の重合体を使用し、試料Ｎｏ．２と同じく１次乾燥緻密化後、抗菌薬剤を付与しない以外同一工程で、スチ−ム弛緩熱処理油剤処理、乾燥・捲縮・バリカットし、３ｄの原綿を得た。
この原綿を日本染色機械（株）製１０Ｋｇオ−バ−マイヤ−染色機のバラ毛キャリヤ−へ詰め込み、浴比１：１０で、ステアリル・アミド・プロピル・ジメチル・ヒドロキシエチル・アンモニウムナイトレ−トを純分で２．０％ｏｗｆ添加し、６０℃から６０分掛けて９８℃まで昇温し、９８℃×６０分間吸着処理を行った。残液を常法のカチオン成分分析エプトン法で完全吸尽を確認した。
その後、常法に従い水洗、油剤処理、乾燥してマラカイトグリ−ン飽和染着量２．１％ｏｗｆの試料Ｎｏ．１３を得た。
次に、試料Ｎｏ．１３ ３０％ ／ウ−ル３０％ ／日本エクスラン工業（株）製Ｋ８０−３ｄ（２０％バルキ−収縮原綿）４０％混からなるバルキ−梳毛綛（１／３６メ−トル番手）を試作した。（試料Ｎｏ．１４）
【００４３】
次に、試料Ｎｏ．１４綛を使用して、Ｂａｙｅｒ（株）製Ｓｕｐｒａｎｏｌ
Ｆａｓｔ Ｂｌａｃｋ ＶＬＧ１．４％ｏｗｆと保土谷化学（株）製Ｃａｔｈ
Ｂｌａｃｋ ＳＢＨ３．５％ｏｗｆ ＰＨ３．５で常法に従い噴射バルキ−染色柔軟処理、乾燥して仕上げた。得られた綛はイラツキもなく良好な黒色を呈していた。（試料Ｎｏ．１５）
また、編地の抗菌性能は、増減値差で洗濯０回：４．６ 洗濯１０回後：５．０で、染色および繰り返し洗濯に対しても極めて耐久性があった。
【００４４】
また、試料Ｎｏ．１４綛を使用して、Ｃｉｂａ−Ｇｙ（株）製 Ｍａｘｉｌｏｎ Ｙｅｌｌｏｗ ＧＬ０．２５％ｏｗｆ，Ｌａｎａｚｏｌ Ｙｅｌｌｏｗ
４Ｇ０．１０％ｏｗｆ ＰＨ４．０で、Ｎｏ．１５と同様に噴射バルキ−染色して仕上げた。得られた綛はくすみもなく鮮明なクリ−ム色を呈していた。（試料Ｎｏ．１６）
また、編地の抗菌性能は、増減値差で洗濯０回：４．８ 洗濯１０回後：５．２で、染色および繰り返し洗濯に対しても極めて耐久性があった。
【００４５】
また、比較例として、薬剤として硝酸銀１．０％ｏｗｆ添加する以外は試料
Ｎｏ．１３と同様に処理し、スルホン酸基に銀が吸着した試料Ｎｏ．１７を得た。
次にＮｏ．１４と同様方法で、綛を試作し、試料Ｎｏ．１６と同一条件で染色し仕上げたが、綛は銀イオンの影響でクリ−ム色が得られず、うす茶色に変色していた。
【００４６】
実施例３
実施例１の試料Ｎｏ．１と同じ組成の重合体、 紡糸原液を作成し、同じ溶剤中に１．５ｄ用口金を用いて押し出し、冷延伸・熱延伸・水洗・一次乾燥緻密化後、抗菌薬剤を付与せずスチ−ム弛緩熱処理（キア−飽和水蒸気１２４℃×７分間）し、油剤・乾燥処理後、二次緊張緻密化処理（乾熱２００℃）し、捲縮・３８ｍｍカットして試料Ｎｏ．１８を得た。
次に、試料Ｎｏ．１８ ５０％／コ−マ綿５０％混からなる綿紡糸（２０／１綿番手）を試作した。
続いて、常法に従って、パイルシ−ツを作成し、ステアリル・アミド・プロピル・ジエチル・メチル・アンモニウムメチルサルフェ−ト純分で１．３％液に２０℃×５秒間ディップし、マングルで水分率７０％に絞り、１００℃×４０分間スチ−ム処理した。（試料Ｎｏ．１９）
次に、日阪製作所（株）製、液流染色機でパイルシ−ツを過酸化水素１５ｇ／ｌｌｐＨ８．５、８０℃×３０分間下晒後、水洗し、続いてＣｉｂａ−Ｇｙ（株）製 Ｍａｘ．Ｒｅｄ ＧＲＬ ０．１％ｏｗｆ ｐＨ３．５で常法に従いアクリル片染め染色、油剤処理、乾燥して仕上げた。（試料Ｎｏ．２０）
得られたパイルシ−ツはきれいな淡ピンク色をしており、また抗菌性能は、増減値差で洗濯０回：４．５、洗濯１０回後：４．３と良好であった。
また比較例として、試料Ｎｏ．１９と同一薬剤条件でディップ、マングルで絞ったパイルシ−ツをスチ−ム吸着処理せずに、パイル用乾燥機で１２５℃×３０分間乾燥した。その後、試料Ｎｏ．２０と同一方法で染色、油剤処理して仕上げたパイルシ−ツは黄変しており、また抗菌性能は不十分であった。（増減値差；洗濯０回：１．５、洗濯１０回後：１．２）
【００４７】
【発明の効果】
上述した本発明の抗菌性アクリロニトリル系繊維は、特定量のスルホン酸基を有するカチオン可染ＡＮ系繊維、または該繊維を含有する繊維製品に対して特定構造の第４級アンモニウム系薬剤を前者の場合には繊維製造工程中、一次緻密化工程の後接触（付与）せしめスチ−ム弛緩熱処理により、また後者の場合には特定温度以上で吸着処理することにより、該繊維内部まで該特定薬剤を浸透、拡散させ、繊維中に薬剤が固定、保持されると考えられる。
このことから、良好な染色性（濃染性：黒、紺、エンジ、緋赤等の染色が可能）を有し、各種製品への加工工程において光、熱、加工薬剤等による変色、着色のない、抗菌性能が染色および繰り返し洗濯によって低下しない抗菌性のカチオン可染ＡＮ系繊維を提供し、且つ該繊維を工業的有利に製造する方法を提供し得たことが本発明の特筆すべき効果である。
この様に優れた利点を有する本発明繊維は、糸、編織物、毛布、ボア類、不織布等に加工することができ、快適な衣料、寝装、インテリア製品、生活資材、産業資材、衣料用繊維資材等の用途分野に広く用いられる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cationic dye-dyeable antibacterial acrylonitrile fiber, a method for producing the fiber, and a method for producing a fiber product comprising the fiber. More specifically, it has good dyeability (dense dyeability), has no discoloration or coloring due to light, heat, processing chemicals, etc. in the processing process to various products, and further has practical performance that does not deteriorate antibacterial performance due to dyeing and washing The present invention provides a method for producing a fiber product having antibacterial properties from a highly cationic dye-dyeable antibacterial acrylonitrile fiber and a method for producing the same, and a fiber product containing the cationic dye-dyeable acrylonitrile fiber.
[0002]
[Prior art]
In recent years, with the maturity and aging of society, and the tendency to demand a rich and comfortable living environment, the demand for maintaining and improving health has increased, and cleaner and more comfortable clothing, bedding, interior products, living materials, etc. Appearance is desired. As one of the methods, various antibacterial fibers have been developed in order to prevent the generation of microorganisms that adversely affect our living environment, to suppress their growth and reproduction, and to maintain a hygienic and clean living environment.
[0003]
As an antibacterial agent to meet such demands, cationic surfactants are well known as reverse soaps, and are related to medical care such as disinfection of hands and surgical departments in hospitals, and hygiene such as sterilization and disinfection in food processing plants. It is used in the direction.
Among cationic surfactants, quaternary ammonium salts have strong bactericidal properties. Typical examples include lauryl, dimethyl, benzyl, ammonium chloride (also known as benzalkonium chloride), which are used for fibers. Organosilicon quaternary ammonium salts are well known as antibacterial agents.
Examples of application of quaternary ammonium salts to acrylonitrile fibers include organosilicon quaternary ammonium salts such as dimethyl octadecyl (3-trimethoxy), as described in JP-B-3-16423. In general, a method of dipping and adsorbing (silyl) -propylammonium chloride to a final fiber product such as after dyeing and bleaching and drying and fixing is used.
In addition, as described in Japanese Patent Publication No. 3-216743, it is stated that a product treated with a quaternary ammonium salt generally has a problem that coloring due to heat is large.
[0004]
When the quaternary ammonium salt is treated in a step before the dyeing process of a cation dye-dyeable acrylonitrile fiber (hereinafter abbreviated as a cation dye AN fiber) having a sulfonic acid group, the sulfonic acid which is a dyeing seat The group is blocked with a quaternary ammonium salt (cation), making it difficult to dye later. Pretreatment of lauryl, dimethyl, benzyl, ammonium chloride and dimethyl, octadecyl, (3-trimethoxysilyl) -propylammonium chloride, which have particularly strong bactericidal and antibacterial properties, on cationic dyeable AN fibers having sulfonic acid groups This causes a problem that the sulfonic acid group of the dyeing seat is strongly blocked, and the dyeability cannot be obtained later. In addition, since the antibacterial site of the quaternary ammonium salt is simultaneously blocked, there arises a problem that the antibacterial performance is lowered.
[0005]
On the other hand, as an example of application to acrylonitrile fiber by a chemical other than quaternary ammonium salt, silver ions or copper ions exhibit excellent antibacterial properties. Methods for imparting antibacterial properties to fibers are known (JP 52-92000, JP 3-199418, etc.). However, they may be colored or discolored due to the influence of light, heat, or chemicals used in various processing steps, and there is a problem that the processing is restricted.
[0006]
[Problems to be solved by the invention]
The present invention was devised in order to solve the problems of the prior art. The object of the present invention is to have good dyeability (dense dyeability), and in the process of processing various products, -Antibacterial properties of cationic dyeable AN fibers that are free from discoloration / coloring due to heat, processing chemicals, etc., and whose antibacterial performance does not deteriorate by dyeing and washing, and their production methods, and fiber products containing cationic dyeable AN fibers The object of the present invention is to provide a production method for producing a textile product with
[0007]
[Means for Solving the Problems]
The object of the present invention described above is to adsorb one or more quaternary ammonium salt-based drugs represented by the following general formula [IV] onto a cationic dyeable AN fiber having a sulfonic acid group of 30 to 80 mmol / Kg. It can be achieved with an antibacterial acrylonitrile fiber characterized in that the saturated dyeing amount of malachite green is 1.1% owf or more.
[0008]
[Formula 4]

[0009]
Further, as a method for obtaining the above-mentioned antibacterial acrylonitrile fiber, it is represented by the following general formula [V] after the primary densification step during the production process of the cationic dyeable AN fiber having a sulfonic acid group of 30 to 80 mmol / Kg. Antibacterial acrylonitrile having a malachite green saturated dyeing amount of 1.1% owf or more by means of contacting one or more of the quaternary ammonium salt chemicals, followed by steam relaxation heat treatment A method for producing a fiber is provided.
[0010]
[Chemical formula 5]

[0011]
In addition, as a method for obtaining a fiber product containing a cationic dyeable AN fiber having antibacterial properties as described above, a fiber product containing a cationic dyeable AN fiber having a sulfonic acid group of 30 to 80 mmol / Kg, Malachite green saturation by means characterized by adsorbing at least one of the quaternary ammonium salt chemicals represented by the general formula [VI] at a temperature of 90 ° C. or higher by an immersion method or a pad steam method. Provided is a method for producing a textile product containing antibacterial acrylonitrile fiber having a dyeing amount of 1.1% owf or more.
[0012]
[Chemical 6]

[0013]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below. Here, the cation dyeable AN fiber having a sulfonic acid group of 30 to 80 mmol / Kg is other vinyl monomer that can be copolymerized with acrylonitrile in an amount of 60% by weight or more, more preferably 80% by weight or more. This refers to a cationic dyeable AN fiber formed from an acrylonitrile copolymer comprising one or more kinds and, if necessary, a desired amount of a sulfonic acid group-containing monomer. Cationic dyeing or cationic dyeable dyeing has an anionic group in a polymer molecule constituting an acrylic fiber, and is ionically bonded with a cationic dye (dissociates to generate a cation) in an aqueous solution. A property that can be done.
[0014]
Examples of vinyl monomers that can be copolymerized with acrylonitrile include vinyl esters such as vinyl acetate; vinyl halides or vinylidenes such as vinyl chloride, vinyl bromide, and vinylidene chloride; methyl acrylate, methyl methacrylate, etc. (Meth) acrylic acid lower alkyl esters (hereinafter (meth) acrylic description represents both acrylic acid and methacrylic acid); acrylamide, styrene and the like.
[0015]
In general, a part of the sulfonic acid group of the acrylonitrile fiber can be filled with a redox catalyst used when polymerizing acrylonitrile, for example, an acid sulfite as a reducing agent bonded to the end of the polymer chain as a sulfonic acid group.
[0016]
The desired amount of the sulfonic acid group-containing monomer here means that an acrylonitrile copolymer having a sulfonic acid group of 30 to 80 mmol / Kg is synthesized, so that only the sulfonic acid group introduced from the above catalyst is insufficient. In some cases, the amount of the sulfonic acid group-containing monomer is copolymerized with acrylonitrile to compensate for this. Moreover, when a redox catalyst is not used, it is necessary to introduce all 30-80 mmol / Kg of sulfonic acid groups from a sulfonic acid group-containing monomer.
[0017]
The sulfonic acid group-containing monomer is not particularly limited as long as it can be copolymerized with acrylonitrile, but methallyl sulfonic acid soda, 2-acrylamido-2-methylpropane sulfonic acid, parastyrene sulfonic acid so- And vinyl sulfonic acid soda.
[0018]
The cationic dyeable acrylonitrile fiber of the starting fiber needs to have 30-80 mmol / Kg of sulfonic acid groups, preferably 40-60 mmol / Kg. This is because if it is less than 30 mmol / Kg, the antibacterial performance and good darkness that do not deteriorate by dyeing and washing as the object of the present invention cannot be obtained. On the other hand, when it exceeds 80 mmol / Kg, the adsorption rate of the quaternary ammonium salt chemical used in the present invention is too high, and there is a disadvantage that uniform treatment cannot be performed. Moreover, the problem that coloring of raw cotton increases (decrease in whiteness) arises.
[0019]
The malachite green saturated dyeing amount of the antibacterial acrylonitrile fiber of the present invention is 1.1% owf or more, preferably 1.3% owf or more. If it is less than 1.1% owf, it is difficult to dye deep colors such as black, wrinkle, engineering, and reddish, which are the object of the present invention, and there is a problem in fastness to dyeing, particularly fastness to wetness.
[0020]
The saturated malachite green dyeing amount referred to in the present invention is dyed under the following conditions, the absorbance is measured by a residual colorimetric method according to a conventional method, the degree of dyeing is obtained by Equation 1, 2, the amount of malachite green saturated dyeing (weight% vs. fiber weight,% owf).
Dye liquor: Malachite green 3.5% owf manufactured by Hodogaya Chemical Co., Ltd.
pH adjuster: Acetic acid 1.5% owf
Bath ratio: 1/100
Temperature: 100 ° C
Time: 150 minutes
Measurement method: Using a U-2000 model manufactured by Hitachi, Ltd., the absorbance with respect to light of 620 nm is measured.
In addition, when the dyeing degree calculated | required by this method exceeds 70%, the malachite green in a dyeing liquid means 5.0% owf and measured again.
[0021]
[Expression 1]

[0022]
[Expression 2]

[0023]
As for the quaternary ammonium salt chemicals according to the present invention, in any of the general formulas [I] to [VI], R1 preferably has 8 to 21 carbon atoms. Moreover, when the carbon number of R1 exceeds 21, in addition to the decrease in antibacterial performance, the dyeability is significantly decreased. The number of carbon atoms in R2 is preferably 2 to 5, and if it exceeds 5, the dyeability is lowered. Further, R3, R4, and R5 preferably have 1 to 5 carbon atoms, and if it exceeds 5, the dyeability is lowered.
[0024]
As the quaternary ammonium salt drug according to the present invention, stearyl / amido / propyl / dimethyl / hydroxyethyl / ammonium nitrate, cetyl / amido / propyl / dimethyl / hydroxyethyl / ammonium nitrate, stearyl / ammonate Amido-propyl-dimethyl-hydroxyethyl-ammonium chloride, cetyl-amide-propyl-dimethyl-hydroxyethyl-ammonium chloride, stearyl-amido-propyl-dimethyl-hydroxyethyl-ammonium bromide, stearyl-amide-ethyl-diethyl-hydroxyethyl Ammonium acetate, stearyl, amide, ethyl, diethyl, hydroxyethyl, ammonium phosphate, stearyl, amide, propyl, dimethyl, Chillyl ammonium ethyl sulfate, cetyl amide propyl dimethyl ethyl ammonium ammonium sulfate, stearyl amide propyl diethyl methyl methyl ammonium methyl sulfate, cetyl amide propyl dimethyl・ Methyl ・ Ammonium Methyl Sulfate, Stearyl ・ Amide ・ Propyl ・ Trimethyl ・ Ammonium Methyl Sulfate, Cetyl ・ Amide ・ Ethyl ・ Diethyl ・ Methyl ・ Ammonium Methyl Sulfate, Stearyl ・ Amide ・ Ethyl ・ Trimethyl ・Ammonium methyl sulfate and the like can be exemplified. Further, the adsorption amount (applied amount) of the drug to the acrylonitrile fiber is 0.2 to 3.0% owf, preferably 0.7 to 2.0% owf. Or several drugs may be mixed.
[0025]
Next, a method for producing the antibacterial acrylonitrile fiber of the present invention will be described. The fiber is produced by chemical treatment during the production process of a cationic dye-dyeable acrylonitrile fiber having a sulfonic acid group of 30 to 80 mmol / Kg. The step of applying the chemical treatment is after the primary densification step.
The term “after the primary densification step in the production process of the cationic dyeable AN fiber having a sulfonic acid group of 30 to 80 mmol / Kg” means after the drying densification step performed after spinning, drawing and washing with water.
In the primary densification step, a stretched tow or filament has a certain amount of moisture (20 to 80% by weight) derived from voids in the fiber. Refers to the process of crushing and densifying the fibers.
This can be done by using a tunnel dryer or drum dryer to remove moisture gradually under high temperature and low humidity conditions, and by using a roller dryer to dry quickly under high temperature dry heat and a certain degree of tension. There are methods.
If the chemical treatment is performed after spinning and before the primary densification step, the fiber structure still has countless holes, so the drug is difficult to fix inside the fiber and falls off in each step until dry densification. There are problems that cause process contamination and drainage abnormalities.
In addition, if the chemical treatment is performed immediately before the primary densification step, the fiber is easily colored in the step performed at a high temperature, which is not preferable in terms of raw cotton whiteness.
[0026]
Further, contacting one or more of the quaternary ammonium salt chemicals described in the present invention means that the tow or filament after the primary densification step in the production process of the acrylonitrile fiber of the present invention is the quaternary salt of the present invention. There is no limitation on the means for contacting with an ammonium salt chemical, and any method such as dip → nip, spray, etc. may be used. A prescription as an example using a crimper-preheating tank or the like is as follows. That is, a target amount for adsorbing the specific drug of the present invention to the tow or filament is added to the processing tank liquid, and then the drug is applied to the tow or filament by using a crimper or the like. The target amount is applied (adsorption), and then the heat is relaxed by steam using a carrier or the like to complete the adsorption.
[0027]
The steam relaxation heat treatment described in the present invention means that the tow of the present invention is relaxed in the steam using a chair or an autoclave. Further, the steam may be continuously relaxed.
The steam is not limited to saturated steam, superheated steam, etc., but it is desirable to treat in saturated steam at 105 ° C to 140 ° C. The degree of relaxation is preferably 5 to 30%.
[0028]
The fiber products containing cationic dyeable AN fibers having a sulfonic acid group of 30 to 80 mmol / Kg according to the present invention include raw cotton (tow, loose hair, etc.), yarn (amber, cheese, etc.), knitted fabric , Blankets / bore, non-woven fabric, etc., and the form is not limited.
[0029]
Further, the treatment by the dipping method referred to in the present invention means that the textile product targeted by the present invention is dipped in a treatment bath containing a predetermined amount of a chemical and processed at a predetermined temperature, preferably Examples thereof include a method that is carried out in the same manner as normal dyeing using a Vermeer dyeing machine or the like.
An example of prescription using an over-myer dyeing machine is as follows. That is, raw cotton (tow, loose hair), etc. is packed into the carrier in the same manner as in normal dyeing, and the target amount for adsorbing the specific agent of the present invention to the raw cotton is added to the tank liquid, and then Adsorption is completed by heating to 90 ° C., heating to boiling, or, if necessary, high temperature and pressure.
[0030]
Also, the treatment by the pad steam method means that the textile product targeted by the present invention is impregnated with a treatment solution containing a predetermined amount of a specific drug, then squeezed with mangles or centrifugally dehydrated, and also only with a spray. It refers to applying a predetermined amount of drug and then steaming.
For example, impregnation with a cationic dyeable AN fiber of the present invention alone, or a sheet, blanket, bored raw fabric, etc. formed by blending the fiber with a target amount for adsorbing the specific agent of the present invention. Adsorption is completed by applying (pickup amount) and then steaming at a temperature of 90 ° C. or higher.
[0031]
[Action]
The antibacterial acrylonitrile fiber according to the present application is a quaternary quaternary structure having a large antibacterial property and a small decrease in dyeability with respect to a specific cationic dyeable AN fiber having a sulfonic acid group of 30 to 80 mmol / Kg. The ammonium salt-based agent is contacted after the primary densification step during the fiber production process, and then subjected to a steam relaxation heat treatment, or by a dipping method or a pad steam method, a temperature higher than the secondary rearrangement temperature of the acrylonitrile fiber. It is considered that the specific antibacterial agent is fixed (bonded to the sulfonic acid group) or retained (loosely bonded to the sulfonic acid group or present in the vicinity of the sulfonic acid group) in the fiber by adsorbing at a temperature of ℃ or higher.
The antibacterial acrylonitrile fiber has a malachite green saturated dyeing amount of 1.1% owf or more, has a good cationic dye dyeing property, that is, a deep dyeing property, and the antibacterial agent penetrates into the fiber. Unlike the general adhesion or fixation to the fiber surface, there is no decrease in antibacterial performance due to dyeing and repeated washing. In addition, in the processing process to various products, light, heat, processing chemicals It is presumed that discoloration and coloring due to the above will decrease.
In addition, the fact that metal ions (silver ions, copper ions) are not used as antibacterial agents is also presumed to be the reason why the above-mentioned discoloration and coloring are few.
Further, the present inventors have found that a compound having a basic structure containing an amide group in the molecule of a quaternary ammonium salt as in the present invention is good as an antibacterial agent having a large antibacterial property and a small decrease in dyeability. Yes.
[0032]
【Example】
Examples are shown below for facilitating the understanding of the present invention. However, these are merely examples, and the gist of the present invention is not limited thereto.
In the examples, parts and percentages are shown on a weight basis unless otherwise specified. In addition, the antibacterial performance, raw cotton whiteness, and washing conditions described in the examples were carried out by the following methods.
[0033]
(1) Antibacterial performance
Test strain: Staphylococcus aureus ATCC 6538P
Test method: In accordance with the method defined by the Textile Products Sanitary Processing Council (SEK), a bouillon suspension of test bacteria is poured into a sterilized sample cloth, and the number of viable bacteria after culturing at 37 ° C for 18 hours in a sealed container is measured. Measured and obtained by the difference in increase / decrease in the number B of the standard cloth and the number C of the sample with respect to the number A of inoculum. Generally, if the increase / decrease value difference is 1.6 or more, it is considered that there is antibacterial performance, but 3.0 or more is preferable.
Increase / decrease value = logC-logA
Increase / decrease value difference = (log B−log A) − (log C−log A)
[0034]
(2) Raw cotton whiteness
MSC-5N manufactured by Suga Test Instruments Co., Ltd. was used, the sample was color-measured under the condition of C light source and twice visual field, the XYZ value was calculated, and the W value (%) was determined by the Judd equation of JIS-1015. Note that the W value (%) is whiter when it is close to 100%.
[0035]
(3) Washing conditions
According to JIS-L-0213 method 103 (for household washing machines), washing is repeated using Monogen Uni manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as a detergent. (10 times, 20 times)
[0036]
Example 1
According to conventional methods, acrylonitrile 91%, acrylic acid methyl ester 9-7%, methallyl sulfonic acid soda 0-2% were changed to synthesize acrylonitrile polymers with different sulfonic acid groups, and a concentration of 46% rhodanso. -A spinning stock solution having a polymer concentration of 12% was prepared by dissolving in an aqueous solution.
The stock solution was extruded into a 10%, -3 ° C aqueous solution of rhodasoda using a known 3d die, and after the cold drawing, hot drawing, water washing and drying densification steps, a crimper-preheating tank was used. At 70 ° C., various quaternary ammonium salt chemicals were added to the running tow weight in a pure amount of 1.5% owf, and then squeezed using a crimper, so that the tank liquid concentration became equilibrium. At this point, the crimped tow was collected, and then steam relaxation heat treatment was performed at 127 ° C. for 7 minutes with a carrier. Sample no. 1-12 were obtained. The amount of sulfonic acid group of each sample and the quaternary ammonium salt chemicals used, evaluation of various properties as antibacterial raw cotton, and 30% antibacterial raw cotton / K8-3d70% blended yarn manufactured by Nippon Exlan Industry Co., Ltd. are used. Various evaluations are made on the prepared knitted fabric, and are also shown in Table 1, Table 2, Table 3, and Table 4.
[0037]
[Table 1]

[0038]
[Table 2]

[0039]
[Table 3]

[0040]
[Table 4]

[0041]
In Table 1 and Table 2, sample Nos. 1, 2, 3, 4 and 5, the amount of the sulfonic acid group of the starting fiber is in the range of 30 to 80 mmol / Kg of the present invention, and the trial production using the specific quaternary ammonium salt chemical of the present invention, In addition, since the saturated dyeing amount of malachite green is 1.1% owf or more of the present invention, all of the deep dyeability, white cotton whiteness and heat resistance are good, and the antibacterial performance is not deteriorated by dyeing and repeated washing. I understand.
On the other hand, sample Nos. Of Comparative Examples in Tables 3 and 4 were used. In No. 6, since the amount of the sulfonic acid group of the starting fiber is small, the deep dyeability is poor, black dyeing is impossible, and the wet fastness is poor. It is also found that the antibacterial dyeing and washing durability is inferior.
Further, sample Nos. Of Comparative Examples in Tables 3 and 4 were used. In No. 7, the amount of sulfonic acid groups in the starting fiber is very large, and uneven adhesion of the antibacterial drug is estimated. Moreover, it turns out that raw cotton whiteness and durability are also inferior.
Furthermore, the sample numbers of Comparative Examples in Tables 3 and 4 are also shown. Although 8, 9, 10, 11, and 12 use a quaternary ammonium salt-based drug, it can be seen that there is a problem with deep dyeing and / or antibacterial performance because it is outside the specific structure of the present invention.
The light resistance of dyed products is generally good because quaternary ammonium salt is used as an antibacterial agent and penetrates and diffuses inside the fiber, not on the fiber surface. Sample No. of Invention Example 1, 2, 3, 4, and 5 were particularly good.
[0042]
Example 2
Sample No. 1 of Example 1 A polymer having the same composition as that of sample No. 2 was used. After the primary drying densification in the same manner as in No. 2, in the same step except that no antibacterial agent was applied, a steam relaxation heat treatment oil treatment, drying / crimping / varicutting was performed to obtain 3d raw cotton.
This raw cotton is packed into a 10-kg over carrier dyeing machine manufactured by Nippon Dyeing Machinery Co., Ltd. 2.0% owf was added as a pure component, the temperature was raised from 60 ° C. to 98 ° C. over 60 minutes, and adsorption treatment was performed at 98 ° C. for 60 minutes. The residual liquid was confirmed to be completely exhausted by the conventional cation component analysis Epton method.
Thereafter, the sample was washed with water, treated with an oil agent and dried according to a conventional method to obtain a sample No. 2 having a malachite green saturated dyeing amount of 2.1% owf. 13 was obtained.
Next, sample No. 13 30% / Wool 30% / Nippon Exlan Industries Co., Ltd. K80-3d (20% bulky-shrinking raw cotton) 40% blended bulky cocoon cocoon (1/36 meter count) was made as a prototype. (Sample No. 14)
[0043]
Next, sample No. Using 14cm, supranol manufactured by Bayer Co., Ltd.
Fast Black VLG 1.4% owf and Hodoya Chemical Co., Ltd. Cath
A black SBH 3.5% owf PH 3.5 was spray-barky-dyed softened according to a conventional method, and finished by drying. The obtained cocoon had a good black color without irritation. (Sample No. 15)
Further, the antibacterial performance of the knitted fabric was 0 times for washing: 4.6 after 10 times for washing: 5.0, and was extremely durable against dyeing and repeated washing.
[0044]
Sample No. Using 14cm, Ciba-Gy Co., Ltd. Maxilon Yellow GL 0.25% owf, Lanazol Yellow
4G0.10% owf PH4.0, No. In the same manner as in No. 15, it was finished by spraying barky dyeing. The resulting cocoon had no dullness and had a clear cream color. (Sample No. 16)
Further, the antibacterial performance of the knitted fabric was 0 times for washing: 4.8 after 10 times for washing: 5.2 in terms of difference in increase and decrease, and was extremely durable against dyeing and repeated washing.
[0045]
In addition, as a comparative example, a sample was added except that 1.0% owf of silver nitrate was added as a drug.
No. The sample No. 13 was treated in the same manner as in No. 13, and silver was adsorbed on the sulfonic acid group. 17 was obtained.
Next, no. A cocoon was made in the same manner as in No. 14, and sample no. Although it was dyed and finished under the same conditions as in No. 16, the cocoon had no cream color due to the influence of silver ions and had turned light brown.
[0046]
Example 3
Sample No. 1 of Example 1 1. Create a polymer and spinning stock solution with the same composition as No. 1, extrude into the same solvent using a 1.5d die, cool drawing, hot drawing, washing with water, primary drying and densification. Relaxation heat treatment (Kia-saturated water vapor 124 ° C. × 7 minutes), oil agent / drying treatment, secondary tension densification treatment (dry heat 200 ° C.), crimping / cutting 38 mm, sample No. 18 was obtained.
Next, sample No. A cotton spun yarn (20/1 cotton count) consisting of 18% 50% / comb cotton 50% was produced.
Subsequently, a pile sheet was prepared according to a conventional method, and dipped into a 1.3% solution of stearyl, amide, propyl, diethyl, methyl, and ammonium methyl sulfate in a 1.3% solution at 20 ° C. for 5 seconds, and then watered with a mangle. The film was squeezed to a rate of 70% and steamed at 100 ° C. for 40 minutes. (Sample No. 19)
Next, the pile sheet was manufactured by Nisaka Seisakusho Co., Ltd. with a liquid dyeing machine, exposed to hydrogen peroxide 15 g / ll pH 8.5 at 80 ° C. for 30 minutes, washed with water, and then manufactured by Ciba-Gy Co., Ltd. Max. Red GRL 0.1% owf pH 3.5 was finished by acrylic dye dyeing, oil treatment, and drying according to a conventional method. (Sample No. 20)
The obtained pile sheet had a beautiful light pink color, and the antibacterial performance was good at 0 times of washing: 4.5 and after 10 times of washing: 4.3 in terms of increase / decrease values.
As a comparative example, Sample No. The pile sheets squeezed with dip and mangle under the same chemical conditions as in No. 19 were dried at 125 ° C. for 30 minutes by a pile dryer without being subjected to steam adsorption treatment. Thereafter, sample No. The pile sheets finished by dyeing and treating with oil in the same manner as in No. 20 were yellowed, and the antibacterial performance was insufficient. (Increase / decrease value difference: 0 times of washing: 1.5, after 10 times of washing: 1.2)
[0047]
【The invention's effect】
The antibacterial acrylonitrile fiber of the present invention described above is a cationic dyeable AN fiber having a specific amount of a sulfonic acid group, or a quaternary ammonium drug having a specific structure for a fiber product containing the fiber. In some cases, during the fiber production process, the specific densification agent is introduced into the fiber by post-contacting (applying) squeezing steam relaxation heat treatment in the primary densification process, or in the latter case by adsorption treatment at a specific temperature or higher. It is considered that the drug is fixed and held in the fiber by infiltration and diffusion.
As a result, it has good dyeability (deep dyeability: black, wrinkle, engineering, dark red, etc. can be dyed). The antibacterial cationic dyeable AN-based fiber whose antibacterial performance is not deteriorated by dyeing and repeated washing, and a method for industrially producing the fiber can be provided. It is.
The fibers of the present invention having such excellent advantages can be processed into yarns, knitted fabrics, blankets, bores, non-woven fabrics, etc., for comfortable clothing, bedding, interior products, living materials, industrial materials, clothing Widely used in application fields such as textile materials.

Claims (3)

One or more quaternary ammonium salt drugs represented by the following general formula [I] are adsorbed on a cationic dye-dyeable acrylonitrile fiber having a sulfonic acid group of 30 to 80 mmol / Kg, and saturated with malachite green. An antibacterial acrylonitrile-based fiber having a dyeing amount of 1.1% owf or more.

One or more quaternary ammonium salt-based chemicals represented by the following general formula [II] after the primary densification step in the production process of the cationic dyeable acrylonitrile fiber having a sulfonic acid group of 30-80 mmol / Kg A method for producing an antibacterial acrylonitrile fiber having a saturated dyeing amount of 1.1% owf or more, characterized in that a thermal relaxation heat treatment is performed after the contact of

One or more quaternary ammonium salt drugs represented by the following general formula [III] are immersed in a fiber product containing a cationic dye-dyeable acrylonitrile fiber having a sulfonic acid group of 30 to 80 mmol / Kg. A method for producing an antibacterial acrylonitrile fiber product having a malachite green saturated dyeing amount of 1.1% owf or more, characterized in that an adsorption treatment is performed at a temperature of 90 ° C. or higher by a pad steam method.