JP3758052B2 - Cotton fiber-containing fiber product and method for producing the same - Google Patents

Description

【０００７】
【化６】

【０００８】
【化７】

【０００９】
【化８】

【００１０】
Ｒ ₀ はＨであり、Ｒ ₁ 、Ｒ ₂ 、Ｒ ₃ 、Ｒ ₄ 、Ｒ ₅ およびＲ ₆ は同種または異なる基であり、それぞれＨ、ＯＨ、ＣＯＯＲ、Ｒ、ＯＲまたはＣＯＯＲのいずれかの基であり、Ｒは炭素数１〜４のアルキル基または置換アルキル基のいずれかを表し、ＸはＣ、ＯまたはＮで、ＸがＯの場合、Ｒ ₃ とＲ ₄ は各々存在せず、ＸがＮの場合、Ｒ ₃ あるいはＲ ₄ が存在しない。
【００１１】
一方、ホルムアルデヒド単独によるセルロースの架橋の場合、架橋長が短かく、架橋歪が残留し、結果として改質に伴なう強力低下が著しい欠点があったが、メチロール化可能な活性水素を有する化合物は、織編物等の布帛の架橋歪を低減させるためのものであり、この効果はホルムアルデヒドによるセルロース間の架橋に加え、該化合物がメチロール化された後セルロースと架橋する、いわゆる架橋長制御により発揮されるものである。このことにより、製品の洗濯後のパッカリング性、保型性等、製品の形態安定性が向上すると同時に引裂強力、抗張力が著しく改善される。さらに、前処理織編物の貯蔵安定性に加え、繊維時のホルマリン臭の低減にも有効である。
【００１２】
上述の如く、予め膨潤前処理による木綿繊維の歪み緩和を計った上での架橋長制御剤に付与によるホルマリン架橋時の架橋歪みの軽減はＷ＆Ｗ性と同時に木綿繊維の力学的特性改善に有効であり本発明に至った。
【００１３】
好適な実施態様としては、架橋改質する改質法が気相ホルマリン加工法であり、また、架橋改質した繊維製品においてその構成する木綿繊維の結合ホルマリン量が０．６重量％以上である。
【００１４】
【発明の実施の形態】
本発明における木綿繊維含有繊維構造物とは木綿１００％はもちろんのこと、他の繊維、例えば苧麻、亜麻、パルプ、バクテリアセルロース繊維等の天然セルロース繊維、絹、羊毛等の天然タンパク繊維、ビスコース法レーヨン（ポリノジックを含む）、銅アンモニア法レーヨン、溶剤紡糸法レーヨン等の再生セルロース繊維、アセテート、トリアセテートなどの半合成繊維、ポリエステル、ポリアミド、アクリル、ポリエチレン、ポリプロピレン等の合成繊維との混繊、混紡、交織、交撚等で混用して得られる紡績糸、織物、編物、不織布等のことである。これら上述の構造物が晒し、反応性染料、バット染料等による先染め、反染、プリント品であってもさしつかえない。他の繊維と混用する場合、本発明の効果をよく発揮させるためには、木綿繊維の含有率は２０重量％以上が好ましく、３０重量％以上がより好ましく、さらに好ましくは５０重量％以上である。
【００１５】
また、本発明で言う繊維製品とは、前記の木綿繊維や混用繊維を用いた織物、編物、不織布等の布帛及びそれを用いて得られたシャツ、スラックス、ブラウス、帽子、ハンカチ等の製品を意味する。
【００１６】
本発明は段落番号００３９に記載した方法による木綿単繊維平行配置繊維束から求められるＸ線配向角は木綿単繊維のＸ線配向角の平均値的な値を示すものであり、本発明では、この値が４５゜以下であり、好ましくは４０゜以下であり、更に好ましくは３５゜以下である木綿単繊維を含む繊維製品である。
【００１７】
木綿繊維のホルムアルデヒドおよび架橋長制御剤による架橋は、予め架橋長制御剤を木綿繊維に付与しておきホルムアルデヒド蒸気（ガス）と二酸化硫黄ガスとを使用するいわゆる気相ホルマリン加工法による方法と予め架橋長制御剤と触媒を木綿繊維に付与しておき、気相ホルマリン加工する方法とが使用できる。
【００１８】
本発明で木綿繊維の歪み緩和に使用できる膨潤剤としては、水酸化リチウム、水酸化カリウム、水酸化ナトリウムなどのアルカリ金属の水酸化物の濃水溶液あるいは液体アンモニア、エチルアミン、ヒドラジンなどがある。これらは木綿繊維を膨潤させると同時に繊維軸方向に張力を支えることが木綿繊維の歪み緩和に有効で結果としてＸ線配向角が小さい値を示す。特に、均一膨潤が計られる液体アンモニア処理や上述のアルカリ土類金属の水酸化物の濃水溶液処理に加え液体アンモニア処理することも有効である。
【００１９】
液体アンモニア処理はドライプロセス（Ｐ．Ｈ．Ｇｒｅｅｎｗｏｏｄ；Ｊ．Ｓ．Ｄ．Ｃ．，１０３ ３４２（１９８７）やウエットプロセス（Ｋ．Ｂｒｅｄｅｒｅｃｋ，Ａ．Ｂｌｕｈｅｒ； Ｍｅｌｌ． Ｔｅｘｔｉｌｂｅｒ．，７２，４４６（１９９１）いずれの方法でも利用できる。また、上述の液体アンモニア処理した後、熱水によるリラックス処理を施してもかまわない。液体アンモニアにより処理する場合、木綿繊維含有織物などの繊維構造物は液体アンモニアに２〜２０秒間浸漬後、５〜９０秒、望ましくは５〜２０秒のタイミングを置いて乾熱、蒸気および水洗によって脱アンモニア処理される。
【００２０】
本発明において水酸化ナトリウムによるアルカリ処理および／または液体アンモニア処理は木綿の原綿、スライバー、紡績糸、生機および布帛のいずれの形態で施してもかまわない。
【００２１】
本発明で使用できる架橋長制御剤は、メチロール化可能な活性水素を有する化合物である。
【００２２】
以下の化９や化１０で示される環状尿素化合物類などが挙げられる。
【００２３】
【化９】

【００２４】
【化１０】

【００２５】
Ｒ₀ はＨであり、Ｒ₁ 、Ｒ₂ 、Ｒ₃ 、Ｒ₄ 、Ｒ₅ およびＲ₆ は同種または異なる基であり、それぞれＨ、ＯＨ、ＣＯＯＲ、Ｒ、ＯＲまたはＣＯＯＲのいずれかの基であり、Ｒは炭素数１〜４のアルキル基または置換アルキル基のいずれかを表し、ＸはＣ、ＯまたはＮで、ＸがＯの場合、Ｒ₃ とＲ₄ は各々存在せず、ＸがＮの場合、Ｒ₃ あるいはＲ₄ が存在しない。
【００２６】
前記の化９および化１０の化合物の内、好ましいメチロール化可能な活性水素を有する化合物としては、エチレン尿素、エチレン尿素／ホルマリン縮合物で両末端がＮＨ基を有するエチレン尿素類、ジヒドロキシエチレン尿素などののジヒドロキシエチレン尿素類が挙げられる。より好ましくは、染色物の耐光性などからジヒドロキシエチレン尿素類が好ましい。これら架橋長制御剤の使用量はセルロースおよび木綿含有繊維構造物に対して、０．５〜２０重量％である。風合いなどを考慮すると更に好ましくは、１〜５重量％である。
【００２７】
本発明で使用できる柔軟剤類としては次のようなものが挙げられる。即ち、ジメチルポリシロキサン、エポキシ変性シリコーン、アミノ変性シリコーン、水溶性シリコーンなどのシリコーン類、ポリエチレンエマルジョン類、脂肪族酸アミド類、ポリウレタン樹脂類、ポリエステル樹脂類、アクリル酸エステル類、ワックス類、ノニオン、アニオン、カチオン、両性の界面活性剤類などが挙げられる。特に、ポリエチレンエマルジョン類、シリコーン類などが風合い向上、引裂強力向上に有効である。
【００２８】
本発明で使用できる潜在性酸性触媒としては、ＡｌＣｌ₃ 、Ａｌ₂ （ＳＯ₄ ）₃ 、ＭｇＣｌ₂ 、Ｍｇ（Ｈ₂ ＰＯ₄ ）₂ 、Ｚｎ（ＢＦ₄ ）₂ 、Ｚｎ（ＮＯ₃ ）₂、ＺｎＣｌ₂ 、Ｍｇ（ＢＦ₄ ）₂ 、Ｍｇ（ＣｌＯ₄ ）₂ 、Ａｌ₂ （ＯＨ）₄ Ｃｌ₂ などの各種金属塩（結晶水含有も含む）類、２−アミノ−２−メチル−１−プロパノールの塩酸塩などの各種アルカノールアミンの酸性塩、硝酸、塩酸、硫酸、りん酸など強酸のアンモニウム塩、蓚酸、クエン酸などの有機カルボン酸などがある。これら潜在性酸性触媒の使用量は０．１〜５重量％である。ホルムアルデヒド蒸気の処理後のキュア条件は、触媒の共存下、通常、２０〜１６０℃で１〜６０分間である。
【００２９】
本発明において架橋反応の程度は、結合ホルマリン量で示されるが、必要であれば結合窒素含有量も合せて示すことができる。本発明の目的を達成するための木綿中の結合ホルマリン量は０．６重量％以上必要である。好ましくは０．８重量％以上である。結合ホルマリン量が０．６重量％未満の場合、十分な改質効果が得られない。即ちパッカリング性、Ｗ＆Ｗ性、保型性、プリーツ性が不十分である。
【００３０】
上記ホルマリン加工により、防しわ性に優れ、かつ繰り返し洗濯後のパッカリング性、Ｗ＆Ｗ性、防縮性、保型性に優れ、同時に加工による強力低下、特に引裂強力低下を極力抑えた木綿繊維含有繊維製品が製造可能となる。
【００３１】
本発明の木綿繊維含有繊維製品は、織物の場合、ＪＩＳ Ｌ−１０５９Ｂ法（モンサント法）における乾防しわ度が２７０度以上であり、湿防しわ度との合計値は５５０度以上が好ましく、５７０度以上がより好ましい。特に乾防しわ度と湿防しわ度との合計値が高い程、Ｗ＆Ｗ性が高くなり、パッカリング性及び保型性にも優れる。これらの防しわ性を達成できるように改質された木綿繊維が含まれる縫製品は、ＡＡＴＣＣ１２４−１９８４法におけるＷ＆Ｗ性が３級以上かＪＩＳ Ｌ−０２１７の１０３法による洗濯５回後のＡＡＴＣＣ法におけるパッカリング性が４級以上の保型性を示す。
【００３２】
本発明におけるセルロースを架橋させることができる薬剤とは、気体、液体、固体、水溶液のいずれでもよいが、加熱等で容易に蒸気となって、木綿繊維内部へ浸透できるものであり、ホルムアルデヒドが好ましい。
【００３３】
セルロースとホルマリンの架橋反応を円滑に進めるためには、木綿繊維中へいかにホルマリンを吸着させるかにつきる。これにはホルマリン気相加工前の縫製品を予め調湿処理することが望ましい。この際の生地水分率は５〜１５重量％が好ましく、より好ましくは６〜１０重量％である。ホルムアルデヒド蒸気の処理条件は、触媒の共存下、通常、８０〜１６０℃で１〜６０分間である。
【００３４】
気相ホルムアルデヒド処理は、布帛の状態及び縫製品の状態のいずれでも処理できるが、縫製品にした後に処理する方が、縫製上の問題発生がなく、縫製品の形状をも効果的に固定するので、パッカリング法、保型性が著しく高くなり、好ましい実施態様である。
【００３５】
【実施例】
以下に本発明を実施例により具体的に説明するが、本発明はこれらの実施例に制限されるものではない。実施例で用いた評価法を以下に示す。
引裂強力；ＪＩＳ Ｌ−１０９６ ペンジュラム法（ヨコ方向）
Ｗ＆Ｗ性；ＡＡＴＣＣ １２４−１９８４ ５段階レプリカ法にもとづいて判定を行った。５級（良好）〜１級（不良）
【００３６】
パッカリング性；ＪＩＳ Ｌ−０２１７ １０３法による洗濯を５回くり返した後、ＡＡＴＣＣ ８８−Ｂ−１９８４法の縫い目５段階レプリカにより評価した。
５級（良好）〜１級（不良）
【００３７】
保型性；ＪＩＳ Ｌ−１０４２ ＦII法による洗濯、タンブル乾燥（Ｉ−２条件）を５回くり返した後、視覚で５段階に判定した。
５（級）：非常に良好
４ 〃 ：良好
３ 〃 ：普通
２ 〃 ：やや不良
１ 〃 ：非常に不良
【００３８】
セルロースＩ型結晶の含有率（％）：木綿単繊維を織編物などの繊維構造物から取り出し、Ｘ線回析法により測定した。測定は、Ｐ．Ｈ．Ｈｅｒｍａｎｓ ＆Ａ．Ｗｅｉｄｉｎｇｅｒ：Ｊ．Ａｐｐｌ．ｐｈｙｓ．，１９，４９１〜５０６（１９４８）およびＢ．Ｇ．Ｒａｎｂｙ：Ａｃｔａ Ｃｈｅｍ．Ｓｃａｃｄ．，６，１１６〜１２７（１９５２）の方法によった。
【００３９】
Ｘ線配向角：製品のよこ糸を分離し、更に木綿単繊維をサンプリングした。
次いで、単繊維の多数本の繊維束を治具の凹部（たて×よこ×奥行＝５ｍｍ×５ｍｍ×１０ｍｍ）に並べセルロイドの希薄溶液を少量加え単繊維同士を平行に並べた後、風乾して測定試料とした。測定は広角Ｘ線回折法により、方位角方向（０〜３６０゜）の走査を行った。Ｊ．Ｊ．Ｇｒｅｅｌｙら：Ｔｅｘｔ．Ｒｅｓ．Ｊ．，２６，７８９（１９５６）では（００２）面を使っているが本発明では、混晶を取り扱うため、ピーク分離しやすい（１０１）面を取り扱うこととし、具体的にはセルロースＩ型結晶の含有率が５０％以上ではセルロースＩ型結晶の（１０１）面に起因する回折ピークの半価幅を、セルロースＩ型結晶の含有率が５０％未満ではセルロース III型結晶の（１０１）面に起因する回折ピークの半価幅をＸ線配向角とした。
【００４０】
結合ホルマリン量：加工布約２ｇを沸水中で１５分間処理し、水洗、絶乾精秤後、水蒸気蒸留法により２０％硫酸中で分解し、亜硫酸水素ナトリウム水溶液中に生成ホルマリンを回収し、よう素滴定法で過剰亜硫酸水素ナトリウムを酸化した後、アルカリで付加物を分解し、ホルマリンと付加した亜硫酸水素ナトリウムの量を求め、加工布の木綿繊維重量あたりのホルマリンを重量％で示した。
【００４１】
実施例１
木綿の紡績糸（４０番手）を綛取りし、この綛を上段・下段のロールにたるまないようにセットし、回転させながら予め、皿に用意した液体アンモニア（−３３．４℃）に各部位が１０秒間浸漬されるよう処理した後、熱風でアンモニアを除去した。こうしてできた紡績糸を緯糸として打ち込んだ木綿織物（４０／１×４０／１／１３５×７５，目付１１４ｇ／ｍ² ）を常法により糊抜・精練・漂白し、次いで液体アンモニアに５秒間浸漬後、７０％の絞り率で搾液し、１０秒間のタイミングをおいた後、１４０℃で１５秒間乾燥した。この加工布（Ａ）を下記組成の加工液（イ）に浸漬し、絞り率７０％になるように絞り、１１０℃で３分間乾燥し、次いでサンフォライズ加工した後、常法によりシャツを縫製した。このシャツの生地水分率を７重量％になるよう調湿し、次いで通常のホルマリン気相加工を施し、本発明のシャツを得た。得られた評価結果を表１に示した。
加工液（イ）
ジヒドロキシエチレン尿素（住友化学工業（株）製） ３重量部
ＭｇＣｌ₂ ・６Ｈ₂ Ｏ（ナカライテクス（株）製試薬） ２重量部
ポリエチレングリコール＃２００（ナカライテスク（株）製ポリエチレング リコール平均分子量２００） ６重量部
パラシリコンＡＹＲ２０（大原パラジウム（株）製シリコ−ン系ソフナ−）４重量部
ＰＥＮ（大日本インキ化学工業（株）製ポリエチレン系ソフナ−）３重量部
水 ８３重量部
【００４２】
実施例２
木綿織物（４０／１×４０／１／１３５×７５，目付１１４ｇ／ｍ² ）の精練・漂白上りを常法により２８°Ｂｅ’のＮａＯＨで水溶液でシルケット加工したのち、液体アンモニア中に５秒間浸漬したのち、７０％の絞り率で搾液し、１５秒のタイミングをおいた後、１４０℃で１５秒間乾燥した。この加工布（Ｂ）を使い、実施例１と同様に加工液（イ）を前処理・サンフォライズ・縫製・ホルマリンによる気相加工を実施した。得られたシャツの評価結果を表１に示した。
【００４３】
実施例３
木綿織物（４０／１×４０／１／１３５×７５，目付１１４ｇ／ｍ² ）の精練・漂白上りを液体アンモニア中に５秒間浸漬したのち、７０％の絞り率で搾液し、１５秒のタイミングをおいた後、１４０℃で１５秒間乾燥した。更に上述の液体アンモニア処理を繰り返し加工布（Ｃ）を得た。この加工布（Ｃ）を使い、実施例１と同様に加工液（イ）を前処理・サンフォライズ加工・縫製・ホルマリンによる気相加工を実施した。得られたシャツの評価結果を表１に示した。
【００４４】
実施例４
木綿織物（８０／２×８０／２／１３４×７６，目付１１３ｇ／ｍ² ）の精練・漂白布を液体アンモニアに５秒間浸漬したのちピンテンターで幅出しをしながらシャワー水洗を繰り返し、次いでテンターで幅出し乾燥した。この液体アンモニア処理工程を２度実施し加工布（Ｄ）を得た。この加工布（Ｄ）を使って実施例１同様に加工液（イ）を前処理・サンフォライズ加工・縫製・ホルマリンによる気相加工を実施した。得られたシャツの評価結果を表１に示した。
【００４５】
比較例１
木綿織物（４０／１×４０／１／１３５／７５、目付１１４ｇ／ｍ² ）の精錬・漂白布（Ｅ）を用いる以外は実施例１と同様に実施した。得られたシャツの評価結果を表１に示した。
【００４６】
比較例２
木綿織物（４０／１×４０／１／１３５×７５，目付１１４ｇ／ｍ² ）の精練・漂白上りを２８°Ｂｅ′のＮａＯＨ水溶液でシルケット加工を施した。この加工布（Ｆ）を用いる以外は実施例１と同様に実施した。得られたシャツの評価結果を表１に示した。
【００４７】
比較例３
実施例１の加工布（Ａ）および加工液（イ）をそれぞれ比較例１の加工布（Ｅ）および下記の加工液（Ｄ）に変更する以外は実施例１と同様に実施した。得られたシャツの評価結果を表１に示した。
加工液（ロ）組成
Ａ−３（高松油脂（株）製ＭｇＣｌ₂ ・６Ｈ₂ Ｏ系架橋触媒） ５重量部
ポリエチレングリコール＃２００（ナカライテクス（株）製ポリエチレン グリコール平均分子量２００） ６重量部
パラシリコンＡＲＹ２０（大原パラジウム（株）製シリコーンソフナー） ４重量部
ＰＥＮ（大日本インキ化学工業（株）製ポリエチレン系ソフナー） ３重量部
水 ８２重量部
【００４８】
比較例４
実施例３の加工布（Ｃ）を用い、ホルマリンによる気相加工時のホルマリン供給量を半分にする以外は実施例１と同様に実施した。得られたシャツの評価結果を表１に示した。
【００４９】
【表１】

【００５０】
本発明のシャツは、風合いが粗硬化せず防しわ性が高く、抗張力の低下が小さく、Ｗ＆Ｗ性に優れ、著しくパッカリング性、保型性に優れる。比較例に示した従来法によるシャツでは、本発明のシャツのように、上記の全ての特性を満足させることは困難である。
【００５１】
【発明の効果】
木綿繊維を膨潤させる薬剤で膨潤させ、同時に木綿繊維の繊維軸方向へ張力をかけ、出来る限り繊維軸方向へ結晶を配向させることによって、木綿繊維の歪みを緩和しておくこと、更には細孔構造（エレメンタリーフィブリル間、ミクロフィブリル間およびラメラ間の間隔）に応じた架橋鎖長を制御するため架橋長制御を予め付与した上でホルマリンによる気相加工すること等により、歪みの発生を極力抑えることが可能となる。こうした木綿繊維を含有する繊維製品は、風合いが良好で、強力低下が少なく、防しわ性が高く、繰り返し洗濯後の優れたＷ＆Ｗ性、防縮性、保型性を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to cellulosic fiber-containing fiber products suitable for clothing such as shirts, slacks and blouses, and as textile goods such as hats and handkerchiefs. More specifically, the strength reduction of the product is suppressed, and shrinkage resistance, W & W (wash) The present invention relates to a cotton fiber-containing fiber product having improved and wear properties, pleating properties, puckering properties, and shape retention properties.
[0002]
[Prior art]
It is a permanent problem to improve the disadvantages of cellulosic fibers, such as wrinkles and shrinkage. For sewn products, especially between fabrics and sewing threads or fabric parts by repeated washing of cellulosic fiber-containing fiber products. There is a strong demand for improvement in the puckering phenomenon (strain phenomenon) caused by the difference in stretchability and the shape retention in the product shape. In order to improve this problem, there is an attempt to use a gas phase reaction with formalin in a product state. However, a new problem that cellulose fiber is significantly reduced in strength is highlighted and a solution is desired.
[0003]
[Problems to be solved by the invention]
The present invention is a cotton having a good texture, excellent in wrinkle resistance, excellent in puckering after repeated washing, W & W property, shrinkage resistance, and shape retention, and at the same time suppressing the reduction in strength due to vapor phase formalin treatment. An object of the present invention is to provide a fiber-containing fiber product and a production method excellent in industrial productivity.
[0004]
[Means for Solving the Problems]
The present inventors pay attention to the fact that the strength of cotton fibers excluding convolution due to underwater untwisting treatment, etc. is higher than before removing the convolution, and the convolution of single fibers in the cotton fabric as an aggregate is performed. I have been studying how to remove it. As a result, the cotton fibers are swollen with a swelling agent, and at the same time, by applying tension in the fiber axis direction and orienting the crystals in the fiber axis direction as much as possible, it is possible to alleviate the distortion of the cotton fibers after crosslinking modification. It has been found that it is effective in suppressing the decrease in strength of cotton fiber products. It was also found that the X-ray orientation angle can be used as an index indicating the degree of strain relaxation here.
[0005]
That is, the present invention is a fiber product obtained by crosslinking and modifying a cotton fiber-containing fiber structure with a cyclic urea compound having an active hydrogen capable of methylolation represented by Chemical Formula 5 or Chemical Formula 6 and formaldehyde, and the constituent fiber of the fiber product. A cotton fiber-containing fiber product having an X-ray orientation angle of 45 ° or less determined from a fiber bundle in which single cotton fibers are arranged in parallel, and a compound having methylol-convertible active hydrogen represented by Chemical Formula 7 or Chemical Formula 8 : And a cotton fiber-containing woven or knitted fabric to which a latent acidic catalyst is applied, or a non-woven fabric, and then a cellulose intermolecular crosslinkable compound is applied to the sewing product and then crosslinked inside the cotton fiber. It is the manufacturing method of the cotton fiber containing fiber product of Claim 1 characterized by the above-mentioned.
[0006]
[Chemical formula 5]

[0007]
[Chemical 6]

[0008]
[Chemical 7]

[0009]
[Chemical 8]

[0010]
R ₀ Is H and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ And R ₆ Are the same or different groups, and each is a group of H, OH, COOR, R, OR or COOR, R represents either an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group, and X represents R ₃ when C, O or N and X is O And R ₄ Are not present, and when X is N, R ₃ Or R ₄ Does not exist.
[0011]
On the other hand, in the case of cross-linking cellulose with formaldehyde alone, the cross-linking length is short, the cross-linking strain remains, and as a result, there is a significant disadvantage that the strength is reduced due to modification. Is for reducing the cross-linking strain of fabrics such as woven and knitted fabrics, and this effect is exhibited by so-called cross-linking length control in which the compound cross-links with cellulose after it is methylolized in addition to cross-linking between formaldehyde and cellulose. It is what is done. This improves the form stability of the product such as puckering and shape retention after washing the product, and at the same time significantly improves the tear strength and tensile strength. Furthermore, in addition to the storage stability of the pretreated woven or knitted fabric, it is also effective in reducing the formalin odor at the time of fiber.
[0012]
As described above, the reduction of cross-linking strain during formalin cross-linking by applying to the cross-linking length control agent after measuring the relaxation of the pre-swelling cotton fiber strain is effective in improving the mechanical properties of cotton fiber as well as W & W properties. Yes, the present invention has been achieved.
[0013]
In a preferred embodiment, the modification method for cross-linking modification is a gas-phase formalin processing method, and the amount of bound formalin of cotton fibers constituting the cross-modified fiber product is 0.6% by weight or more. .
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The cotton fiber-containing fiber structure in the present invention is not only 100% cotton, but also other fibers such as natural cellulose fibers such as linseed, flax, pulp and bacterial cellulose fibers, natural protein fibers such as silk and wool, viscose. Recycled cellulose fibers such as rayon (including polynosic), copper ammonia rayon, solvent spinning rayon, semi-synthetic fibers such as acetate and triacetate, blends with synthetic fibers such as polyester, polyamide, acrylic, polyethylene and polypropylene, A spun yarn, woven fabric, knitted fabric, non-woven fabric, etc. obtained by blending, blending, knitting, etc. Even if these above-mentioned structures are exposed, they can be dyed with reactive dyes, vat dyes, anti-dyes or printed products. When used in combination with other fibers, the content of the cotton fibers is preferably 20% by weight or more, more preferably 30% by weight or more, and still more preferably 50% by weight or more in order to exhibit the effects of the present invention well. .
[0015]
In addition, the fiber products referred to in the present invention include fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics using the above-described cotton fibers and mixed fibers, and products such as shirts, slacks, blouses, hats, handkerchiefs, and the like. means.
[0016]
In the present invention, the X-ray orientation angle obtained from the single-fiber-fabric parallel-arranged fiber bundle according to the method described in Paragraph 0039 indicates an average value of the X-ray orientation angles of the single cotton fibers. This value is 45 ° or less, preferably 40 ° or less, more preferably 35 ° or less.
[0017]
Crosslinking of cotton fiber with formaldehyde and a crosslinking length control agent is carried out in advance by a so-called gas phase formalin processing method in which a crosslinking length control agent is previously applied to cotton fiber and formaldehyde vapor (gas) and sulfur dioxide gas are used. It is possible to use a method in which a long control agent and a catalyst are applied to a cotton fiber, and gas phase formalin processing is performed.
[0018]
Examples of the swelling agent that can be used for relaxation of cotton fiber strain in the present invention include concentrated aqueous solutions of alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide, liquid ammonia, ethylamine, and hydrazine. These swell the cotton fibers and at the same time support the tension in the fiber axis direction is effective in relaxing the distortion of the cotton fibers, resulting in a small X-ray orientation angle. In particular, it is also effective to carry out liquid ammonia treatment in addition to the liquid ammonia treatment in which uniform swelling is measured or the concentrated aqueous solution treatment of the above-mentioned alkaline earth metal hydroxide.
[0019]
Liquid ammonia treatment can be performed by a dry process (PH Greenwood; JSDC, 103 342 (1987) or a wet process (K. Brederec, A. Bluher; Mell. Textilber., 72, 446 (1991)). Any of the methods can be used, and after the above-described liquid ammonia treatment, a relaxation treatment with hot water may be performed. After immersing for ˜20 seconds, deammonia treatment is performed by dry heat, steam and water washing at a timing of 5 to 90 seconds, preferably 5 to 20 seconds.
[0020]
In the present invention, the alkali treatment with sodium hydroxide and / or the liquid ammonia treatment may be performed in any form of cotton raw cotton, sliver, spun yarn, raw machinery and fabric.
[0021]
Crosslinking length control agent that can be used in the present invention, Ru compound der having a methylolated active hydrogen capable.
[0022 ]
Cyclic urea compounds represented by the formula 9 arrows of 10 follows and the like.
[0023]
[Chemical 9]

[0024]
[Chemical Formula 10]

[0025]
R ₀ is H, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are the same or different groups, and each is a group of H, OH, COOR, R, OR or COOR. And R represents either an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group, X is C, O or N, and when X is O, R ₃ and R ₄ are not present, and X is In the case of N, R ₃ or R ₄ does not exist .
[0026]
Among the compounds of the above formula 9 and formula 10, the compound having a preferred methylolated active hydrogen capable, ethylene urea, ethylene ureas both ends with ethylene urea / formaldehyde condensate having a NH group, dihydroxy ethylene urea dihydroxy ethylene ureas Do Dono thereof. More preferably, dihydroxyethylene ureas are preferable from the light resistance of the dyed product. The usage-amount of these crosslinking length control agents is 0.5 to 20 weight% with respect to a cellulose and cotton containing fiber structure. Considering the texture and the like, it is more preferably 1 to 5% by weight.
[0027]
Examples of softeners that can be used in the present invention include the following. That is, silicones such as dimethylpolysiloxane, epoxy-modified silicone, amino-modified silicone, water-soluble silicone, polyethylene emulsions, aliphatic acid amides, polyurethane resins, polyester resins, acrylic esters, waxes, nonions, Anionic, cationic, amphoteric surfactants and the like can be mentioned. In particular, polyethylene emulsions, silicones and the like are effective in improving the texture and tearing strength.
[0028]
Examples of the latent acidic catalyst that can be used in the present invention include AlCl ₃ , Al ₂ (SO ₄ ) ₃ , MgCl ₂ , Mg (H ₂ PO ₄ ) ₂ , Zn (BF ₄ ) ₂ , Zn (NO ₃ ) ₂ , ZnCl ₂ , Mg (BF ₄ ) ₂ , Mg (ClO ₄ ) ₂ , Al ₂ (OH) ₄ Cl ₂ and other metal salts (including crystal water), 2-amino-2-methyl-1-propanol There are acid salts of various alkanolamines such as hydrochlorides, ammonium salts of strong acids such as nitric acid, hydrochloric acid, sulfuric acid and phosphoric acid, and organic carboxylic acids such as oxalic acid and citric acid. The amount of these latent acidic catalysts used is 0.1 to 5% by weight. Cure conditions after the treatment with formaldehyde vapor are usually 20 to 160 ° C. for 1 to 60 minutes in the presence of the catalyst.
[0029]
In the present invention, the degree of the crosslinking reaction is indicated by the amount of bound formalin, but if necessary, the bound nitrogen content can also be indicated. In order to achieve the object of the present invention, the amount of bound formalin in cotton needs to be 0.6% by weight or more. Preferably it is 0.8 weight% or more. When the amount of bound formalin is less than 0.6% by weight, a sufficient reforming effect cannot be obtained. That is, puckering property, W & W property, shape retention property, and pleat property are insufficient.
[0030]
The above-mentioned formalin processing is excellent in wrinkle resistance, and has excellent puckering after repeated washing, W & W properties, shrinkage resistance, and shape retention, and at the same time, a fiber containing cotton fibers that suppresses the decrease in strength due to processing, especially tear strength. The product can be manufactured.
[0031]
In the case of textile, the cotton fiber-containing fiber product of the present invention has a dry wrinkle degree of 270 degrees or more in the JIS L-1059B method (Monsanto method), and the total value of the moisture prevention wrinkle degree is preferably 550 degrees or more, 570 degree | times or more are more preferable. In particular, the higher the total value of the dry proof wrinkle degree and the wet proof wrinkle degree, the higher the W & W property and the better the puckering property and the shape retaining property. Sewing products containing cotton fibers modified so as to achieve these wrinkle-proofing properties have a W & W property of grade 3 or higher in the AATCC 124-1984 method or the AATCC method after 5 washes according to the 103 method of JIS L-0217 The puckering property at 4 indicates a shape retention property of grade 4 or higher.
[0032]
The agent capable of cross-linking cellulose in the present invention may be any of gas, liquid, solid, and aqueous solution, but is easily vaporized by heating or the like and can penetrate into cotton fibers, and formaldehyde is preferable. .
[0033]
In order to facilitate the cross-linking reaction between cellulose and formalin, it depends on how formalin is adsorbed into cotton fibers. For this purpose, it is desirable to preliminarily humidity-treat the sewing product before formalin gas phase processing. In this case, the moisture content of the dough is preferably 5 to 15% by weight, more preferably 6 to 10% by weight. The processing conditions for formaldehyde vapor are usually 80 to 160 ° C. for 1 to 60 minutes in the presence of the catalyst.
[0034]
Vapor-phase formaldehyde treatment can be performed in either fabric state or sewing product state, but processing after making it into a sewing product will not cause any problems in sewing and will effectively fix the shape of the sewing product. Therefore, the puckering method and the shape retention are remarkably enhanced, which is a preferred embodiment.
[0035]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The evaluation methods used in the examples are shown below.
Tearing strength: JIS L-1096 pendulum method (horizontal direction)
W & W property: AATCC 124-1984 Judgment was made based on the 5-step replica method. Grade 5 (good) to Grade 1 (bad)
[0036]
Packing property: After repeating washing by JIS L-0217 103 method 5 times, it was evaluated by 5-step replica of seam of AATCC 88-B-1984 method.
Grade 5 (good) to Grade 1 (bad)
[0037]
Shape retention: Washing by JIS L-1042 FII method and tumble drying (I-2 condition) were repeated 5 times, and then visually judged in 5 stages.
5 (Class): Very good 4 ：: Good 3 〃: Normal 2 〃: Slightly bad 1 〃: Very bad [0038]
Cellulose I-type crystal content (%): Cotton single fiber was taken out from a fiber structure such as a woven or knitted fabric and measured by an X-ray diffraction method. The measurement was performed on P.I. H. Hermans & A. Weidinger: J.M. Appl. phys. 19, 491-506 (1948) and B.I. G. Ranby: Acta Chem. Scacc. 6, 116-127 (1952).
[0039]
X-ray orientation angle: Weft yarns of the product were separated, and cotton single fibers were sampled.
Next, a large number of fiber bundles of single fibers are arranged in the recesses of the jig (vertical x width x depth = 5 mm x 5 mm x 10 mm), a small amount of dilute solution of celluloid is added, the single fibers are arranged in parallel, and then air-dried. The measurement sample was used. The measurement was performed by scanning in the azimuth direction (0 to 360 °) by a wide angle X-ray diffraction method. J. et al. J. et al. Greery et al .: Text. Res. J. et al. , 26, 789 (1956) uses the (002) plane. However, in the present invention, since the mixed crystal is handled, the (101) plane which is easily separated into peaks is handled. Specifically, the inclusion of cellulose type I crystals is included. When the ratio is 50% or more, the half-value width of the diffraction peak due to the (101) plane of the cellulose I-type crystal is caused, and when the content of the cellulose I-type crystal is less than 50%, the half-width is caused by the (101) plane of the cellulose III-type crystal. The half width of the diffraction peak was taken as the X-ray orientation angle.
[0040]
Bonded formalin amount: About 2 g of processed cloth is treated in boiling water for 15 minutes, washed with water, completely dried and weighed, then decomposed in 20% sulfuric acid by steam distillation method, and recovered formalin is recovered in aqueous sodium hydrogen sulfite solution. Excess sodium bisulfite was oxidized by the basic titration method, then the adduct was decomposed with alkali, the amount of formalin and added sodium bisulfite was determined, and the formalin per weight of cotton fiber of the processed cloth was expressed in wt%.
[0041]
Example 1
Take the cotton spun yarn (No. 40), set it so that it does not sag on the upper and lower rolls, and rotate each piece into the liquid ammonia (-33.4 ° C) prepared in advance in a dish. Was soaked for 10 seconds, and then ammonia was removed with hot air. A cotton fabric (40/1 × 40/1/135 × 75, basis weight 114 g / m ² ) driven with the spun yarn thus produced as a weft is desizing, scouring and bleaching by a conventional method, and then immersed in liquid ammonia for 5 seconds. Thereafter, the solution was squeezed at a squeezing rate of 70%, set for 10 seconds, and then dried at 140 ° C. for 15 seconds. This processed cloth (A) was dipped in a processing liquid (I) having the following composition, drawn to a drawing ratio of 70%, dried at 110 ° C. for 3 minutes, then subjected to sanforization, and then a shirt was sewn in a conventional manner. . The shirt was conditioned to a moisture content of 7% by weight, and then subjected to normal formalin vapor phase processing to obtain the shirt of the present invention. The obtained evaluation results are shown in Table 1.
Processing fluid (I)
Dihydroxyethylene urea (manufactured by Sumitomo Chemical Co., Ltd.) 3 parts by weight MgCl ₂ .6H ₂ O (reagent manufactured by Nacalai Tex Co., Ltd.) 2 parts by weight polyethylene glycol # 200 (polyethylene glycol average molecular weight 200 manufactured by Nacalai Tesque Co., Ltd.) ) 6 parts by weight Parasilicon AYR20 (Silicon softener manufactured by Ohara Palladium Co., Ltd.) 4 parts by weight PEN (polyethylene softener manufactured by Dainippon Ink and Chemicals) 3 parts by weight Water 83 parts by weight
Example 2
A cotton fabric (40/1 × 40/1/135 × 75, basis weight 114 g / m ² ) was scoured and bleached and then mercerized with an aqueous solution of 28 ° Be ′ NaOH in a conventional manner, and then placed in liquid ammonia for 5 seconds. After dipping, the solution was squeezed at a squeezing rate of 70%, and after 15 seconds, it was dried at 140 ° C. for 15 seconds. Using this work cloth (B), in the same manner as in Example 1, the working liquid (i) was subjected to gas phase processing by pretreatment, sun folize, sewing and formalin. The evaluation results of the obtained shirt are shown in Table 1.
[0043]
Example 3
A cotton fabric (40/1 × 40/1/135 × 75, basis weight 114 g / m ² ) is squeezed and bleached for 5 seconds and then squeezed at 70% squeezing rate for 15 seconds. After timing, the film was dried at 140 ° C. for 15 seconds. Furthermore, the above-mentioned liquid ammonia treatment was repeated to obtain a processed cloth (C). Using this processed cloth (C), the processing liquid (I) was pretreated, sanforized, sewn, and vapor-phase processed by formalin in the same manner as in Example 1. The evaluation results of the obtained shirt are shown in Table 1.
[0044]
Example 4
After scouring a cotton fabric (80/2 × 80/2/134 × 76, basis weight 113 g / m ² ) and immersing the bleached fabric in liquid ammonia for 5 seconds, repeating washing with shower water with a pin tenter, and then using a tenter Tentered and dried. This liquid ammonia treatment process was performed twice to obtain a processed cloth (D). Using this processed cloth (D), the processing liquid (I) was pretreated, sanforized, sewn, and vapor-phase processed by formalin in the same manner as in Example 1. The evaluation results of the obtained shirt are shown in Table 1.
[0045]
Comparative Example 1
The same procedure as in Example 1 was performed except that a cotton fabric (40/1 × 40/1/135/75, basis weight 114 g / m ² ) refining and bleaching fabric (E) was used. The evaluation results of the obtained shirt are shown in Table 1.
[0046]
Comparative Example 2
A cotton fabric (40/1 × 40/1/135 × 75, basis weight 114 g / m ² ) was scoured and bleached, and then subjected to mercerization with a 28 ° Be ′ NaOH aqueous solution. It implemented like Example 1 except using this work cloth (F). The evaluation results of the obtained shirt are shown in Table 1.
[0047]
Comparative Example 3
The same procedure as in Example 1 was performed except that the processed cloth (A) and the processed liquid (I) in Example 1 were changed to the processed cloth (E) in Comparative Example 1 and the following processed liquid (D), respectively. The evaluation results of the obtained shirt are shown in Table 1.
Working fluid (b) Composition A-3 (MgCl ₂ · 6H ₂ O-based cross-linking catalyst manufactured by Takamatsu Yushi Co., Ltd.) 5 parts by weight Polyethylene glycol # 200 (Nacalai tex Co., Ltd. polyethylene glycol average molecular weight 200) 6 parts by weight Silicon ARY20 (Ohara Palladium Silicone Softener) 4 parts by weight PEN (Dainippon Ink & Chemicals Polyethylene Softener) 3 parts by weight Water 82 parts by weight
Comparative Example 4
It was carried out in the same manner as in Example 1 except that the work cloth (C) of Example 3 was used and the formalin supply amount during gas phase processing with formalin was halved. The evaluation results of the obtained shirt are shown in Table 1.
[0049]
[Table 1]

[0050]
The shirt of the present invention does not roughen the texture and has high wrinkle resistance, small reduction in tensile strength, excellent W & W properties, and remarkably excellent puckering properties and shape retention properties. In the shirt according to the conventional method shown in the comparative example, it is difficult to satisfy all the above characteristics as in the shirt of the present invention.
[0051]
【The invention's effect】
Swell the cotton fiber with an agent that swells it, and at the same time apply tension in the fiber axis direction of the cotton fiber to orient the crystals in the fiber axis direction as much as possible, thereby relaxing the strain of the cotton fiber and further reducing the pores. In order to control the cross-linking chain length according to the structure (inter-elementary fibrils, micro-fibrils, and lamellas), the cross-linking length control is given in advance, and then the formation of strain is minimized by performing gas phase processing with formalin. It becomes possible to suppress. Such a fiber product containing cotton fibers has a good texture, little reduction in strength, high wrinkle resistance, and excellent W & W properties, shrinkage resistance, and shape retention after repeated washing.

Claims (3)

A cotton single fiber which is a fiber product obtained by crosslinking and modifying a cotton fiber-containing fiber structure with a cyclic urea compound having an active hydrogen capable of methylolation represented by chemical formula 1 or chemical formula 2 and formaldehyde, and is a constituent fiber of the textile product A cotton fiber-containing fiber product having an X-ray orientation angle of 45 ° or less determined from a bundle of fibers arranged in parallel.

R ₀ Is H and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ And R ₆ Are the same or different groups, and each is a group of H, OH, COOR, R, OR or COOR, R represents either an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group, and X represents R ₃ when C, O or N and X is O And R ₄ Are not present, and when X is N, R ₃ Or R ₄ Does not exist.  The cotton fiber-containing content according to claim 1, wherein the binding formalin amount of the cotton fiber by cross-linking modification is 0.6% by weight or more, and the puckering property after repeated washing 5 times by JIS L-0217 103 method is 4th or more. Fiber products. Sewing using a cotton fiber-containing woven or knitted fabric having a cyclic urea compound having a methylolizable active hydrogen represented by Chemical Formula 3 or Chemical Formula 4 and a latent acidic catalyst, or a nonwoven fabric, and then capable of crosslinking between cellulose molecules 2. The method for producing a cotton fiber-containing fiber product according to claim 1, wherein the compound is imparted to the sewing product and then crosslinked inside the cotton fiber.

R ₀ Is H and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ And R ₆ Are the same or different groups, and each is a group of H, OH, COOR, R, OR or COOR, R represents either an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group, and X represents R ₃ when C, O or N and X is O And R ₄ Are not present, and when X is N, R ₃ Or R ₄ Does not exist.