JP2004218117A

JP2004218117A - Hygroscopically exothermic cellulosic fiber and woven/knitted fabric

Info

Publication number: JP2004218117A
Application number: JP2003005159A
Authority: JP
Inventors: Takeo Shimizu; 壮夫清水
Original assignee: Unitika Textiles Ltd
Current assignee: Unitika Textiles Ltd
Priority date: 2003-01-10
Filing date: 2003-01-10
Publication date: 2004-08-05

Abstract

<P>PROBLEM TO BE SOLVED: To obtain hygroscopically exothermic cellulosic fibers having excellent hygroscopically exothermic tendency, high in laundering durability and producible through easy processability at low cost by utilizing a hydrazine derivative bearing at least two hydrazido groups in the molecule, a silicone compound and a natural moisturizing component. <P>SOLUTION: In the hygroscopically exothermic cellulosic fibers, at least one hydrazido group of a compound bearing at least two hydrazido groups in the molecule is chemically bound to the hydroxy group in the cellulose molecule, or one reactive functional group of a compound bearing at least two reactive functional groups in the molecule is chemically bound to the hydroxy group in the cellulose molecule and the other reactive functional group is chemically bound to the hydrazido group of a hydrazine compound. The cellulosic fibers and the cellulosic woven/knitted fabrics comprising the cellulosic fibers can be imparted with hygroscopically exothermic tendency with high laundering durability by sticking the silicone compound and the natural moisturizing component onto the fibers. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【０００１】
【発明の属する技術分野】
本発明は、水分を吸収し発熱する機能を有する吸湿発熱性セルロース系繊維及び織編物に関するものである。
【０００２】
【従来の技術】
従来から秋冬保温衣料として、遠赤外線放射素材や蓄熱保温素材が展開され、特にスポーツ・アウトドア分野、例えばスキーウエア，ウインドブレーカー，ブルゾンなどの防寒衣料に広く採用されている。これらの素材は、保温機能は優れているものの、太陽光の射さない場所では機能が低下するといった問題から主にアウター用途に限定使用され、運動時の発汗による冷え感防止というインナー用途への潜在的ニーズを抱えたままでいた。
この問題を解決するため、身体又は外気から水分を吸収する際に熱エネルギーを発生する吸湿発熱素材が開発され、外部環境によらず優れた保温機能を発現するだけでなく、冷え性や寒がりに悩む消費者から切望されていたインナー用途への展開も可能となった。
【０００３】
この吸湿発熱素材には、糸条にその機能を有する例として、親水基を有する化学変性体を高密度で強架橋したアクリレート繊維糸条を用いて作製された織編物（例えば、特許文献１参照）、また後加工で該機能を付与する例として、セルロース繊維を一成分として含む織編物に対し、セルロース分子の水酸基にＮ−メチロール（メタ）アクリルアミド（Ｎ−ＭＡＭ）を結合させ、次いでＮ−ＭＡＭのビニル基を開始点として重合性ビニル化合物を重合する方法（例えば、特許文献２参照）や、セルロース系織編物へ分子中に少なくとも３個のカルボキシル基を有するポリカルボン酸を反応させ、アルカリ金属塩の水溶液でソーピングする方法（例えば、特許文献３参照）などが提案されている。
【０００４】
これらの吸湿発熱素材は、いずれも身体から発生する汗などの水分や外部環境の変化によって生じた結露などの湿気を吸収し、熱エネルギーに変換する作用を奏するもので、基材となる繊維素材が元来有する機能・風合いを保持しており、アウター用途以外にもインナー、さらにはソックス・ヘアバンド・帽子などの小物への展開も図ることができる。
しかし、いずれの吸湿発熱素材もその製法が複雑であって、高コストという課題を残している。上記特許文献１にかかる発明は、アクリレート繊維分子へ、親水基を有する化学変性体で高密度かつ強架橋することで初めてかかる機能を奏するものであって、加工条件がシビアな上、該化学変性体により糸条がうっすらと着色されるため、染色の色振れが生じやすいという問題を内在している。
また、上記特許文献２にかかる発明は、かかる機能の根幹をなす重合物を、加工途中において織編物上で生成させるために条件がシビアな上性能にバラツキが生じやすい。
一方、上記特許文献３にかかる発明は、条件はシビアでないもののポリカルボン酸での処理に続きアルカリ金属塩の水溶液でソーピングするという２つの処理工程を経なければならず、高コストという課題を残している。
【０００５】
【特許文献１】
特公平７−５９７６２号公報（〔００１５〕及び〔００１７〕）
【特許文献２】
特許第２８９８６２３号公報（請求項６及び〔０００８〕）
【特許文献３】
特開２０００−２５６９６２号公報（請求項１）
【０００６】
【発明が解決しようとする課題】
本発明は、このような課題を解決するものであり、分子中に少なくとも２個のヒドラジド基を有するヒドラジン誘導体と、シリコーン化合物及び天然保湿成分を応用することにより優れた吸湿発熱性を持ち、かつ洗濯耐久性にも優れ、さらに易加工性，低コストで製造できる吸湿発熱性セルロース系繊維を得ることを技術的課題とする。
【０００７】
【課題を解決するための手段】
本発明者は、上記の目的を達成するため鋭意研究の結果、ヒドラジン化合物の吸湿性に着目し、分子中に少なくとも２個以上のヒドラジド基を有する化合物の少なくとも１つのヒドラジド基がセルロース分子の水酸基と化学結合する、又は分子中に少なくとも２個の反応性官能基を有する化合物の１つの反応性官能基がセルロース分子の水酸基と化学結合し、かつもう１つの反応性官能基がヒドラジン化合物のヒドラジド基と化学結合する、あるいはシリコーン化合物及び天然保湿成分を繊維上に固着すればセルロース系繊維及びセルロース系織編物へ洗濯耐久性に優れた吸湿発熱性が付与できることを見出し、本発明に到達した。
すなわち、本発明は以下の（１）〜（１３）要旨とするものである。
【０００８】
（１）分子中に少なくとも２個のヒドラジド基を有するヒドラジン誘導体が固着されていることを特徴とする吸湿発熱性セルロース系繊維。
（２）前記ヒドラジン誘導体が、基材であるセルロース系繊維重量に対し０．５〜２０重量部固着されていることを特徴とする（１）記載の吸湿発熱性セルロース系繊維。
さらに、好ましい態様として以下が含まれる。
（３）分子中に少なくとも２個の反応性官能基を有する化合物を介して前記ヒドラジン誘導体が、基材であるセルロース系繊維へ固着されていることを特徴とする（１）又は（２）記載の吸湿発熱性セルロース系繊維。
（４）前記少なくとも２個の反応性官能基を有する化合物が、少なくともエポキシ樹脂，アミノプラスト樹脂もしくはイソシアネート樹脂のいずれかを含む成分から構成されていることを特徴とする（３）記載の吸湿発熱性セルロース系繊維。
（５）シリコーン系化合物及び天然保湿成分が固着されていることを特徴とする吸湿発熱性セルロース系繊維。
（６）前記シリコーン系化合物及び前記天然保湿成分が被覆されていることを特徴とする（４）記載の吸湿発熱性セルロース系繊維。
（７）（１）〜（６）のいずれかに記載の吸湿発熱性セルロース系繊維を少なくとも構成糸の一部とすることを特徴とする織編物。
【０００９】
一方、公知のセルロース系織編物を用いて、後加工を施すことで吸湿発熱性を付与する態様として、以下が含まれる。
（８）セルロース系繊維を少なくとも構成糸の一部とする織編物であって、該織編物全体に渡って前記ヒドラジン誘導体が固着されていることを特徴とする吸湿発熱性セルロース系織編物。
（９）前記ヒドラジン誘導体が、基材であるセルロース系織編物重量に対し０．５〜２０重量部固着されていることを特徴とする（８）記載の吸湿発熱性セルロース系織編物。
（１０）セルロース系繊維を少なくとも構成糸の一部とする織編物であって、該織編物全体に渡って前記ヒドラジン誘導体が、前記分子中に少なくとも２個の反応性官能基を有する化合物を介して固着されていることを特徴とする吸湿発熱性セルロース系織編物。
（１１）前記少なくとも２個の反応性官能基を有する化合物が、少なくともエポキシ樹脂，アミノプラスト樹脂もしくはイソシアネート樹脂のいずれかを含む成分から構成されていることを特徴とする（１０）記載の吸湿発熱性セルロース系織編物。
（１２）セルロース系繊維を少なくとも構成糸の一部とする織編物であって、該織編物全体に渡って前記シリコーン系化合物及び前記天然保湿成分が固着されていることを特徴とする吸湿発熱性セルロース系織編物。
（１３）前記シリコーン系化合物及び前記天然保湿成分が被覆されていることを特徴とする請求項１１記載の吸湿発熱性セルロース系織編物。
【００１０】
【発明の実施の形態】
以下、本発明を詳説する。
本発明の吸湿発熱性セルロース系繊維は、セルロース系繊維を付帯加工することで得られる。かかるセルロース系繊維とは、セルロース繊維を主成分にする繊維糸条を指す。セルロース繊維とは、例えば天然繊維の場合は綿，麻など、再生繊維の場合は、ビスコースレーヨン，キュプラ，溶剤紡糸セルロース繊維などがあげられる。繊維形態は長・短繊維のいずれでもよく、繊度・繊維長は特に限定されない。
【００１１】
本発明に供するセルロース系繊維目的に応じこれらの繊維を単独又は複数混合、あるいは前記セルロース繊維の内選択された一種以上の繊維と一種以上の他糸を混合して使用する。混合する他糸は、例えば羊毛，絹などの天然繊維、ポリエステル，ポリアミド，アクリル，ポリウレタン，ポリオレフィンなどの合成繊維、トリアセテートなどの半合成繊維などがあげられ、目的・用途に応じ繊維形態は長・短繊維のいずれでもよく、繊度・繊維長も特に限定されない。
【００１２】
混合方法及び混合比率は特に限定されず、混合する繊維が短繊維のみから構成される場合、混紡糸として供するなら、例えば混打綿工程でそれぞれの繊維を混ぜ合わせ、カード，練条，粗紡，精紡を経る方法、もしくはそれぞれの繊維を単独でカード工程まで紡績した後、練条工程にてスライバーで合せる方法、又はそれぞれの繊維を単独に練条した複数のスライバーを引き揃えて粗紡・精紡する方法などがある。意匠性を向上したい場合は、光沢を有する繊維や既に染着された繊維などを使用する。例えば繊維製造時に着色剤を混用して製造した原着糸又は先染糸、あるいは光沢の異なる異型断面糸又は艶消剤の含有量が異なる繊維などを適当量混ぜることで、染色後に光沢や色相の異なる杢感を表現できる。
一方、複合糸として供するなら、該複合糸を構成する糸条のスライバーを公知法に準じて用意し粗紡工程にて複合する方法、あるいは該複合糸を構成する糸条の粗糸を用意し精紡工程にて複合する方法があげられる。いずれの方法も給糸間にフィード差を設けることで芯鞘構造糸とすることができ、フィード差を設けなければ、交撚糸とすることができる。
【００１３】
混合する繊維が長繊維及び短繊維から構成される場合は、長繊維糸条及び公知法で作製された短繊維粗糸をそれぞれ用意し、精紡工程を経て製造される。この方法も上記と同じく、給糸間にフィード差を設けることで芯鞘構造糸とすることができ、フィード差を設けなければ、交撚糸とすることができる。
一方、混合する繊維が長繊維のみから構成される場合は、それぞれの糸条をパーンワインダーにて引き揃える、空気混繊する、あるいは合撚機にて施撚された形態で混合するなどの態様があげられる。
【００１４】
以上、本発明に供されるセルロース系繊維は目的に応じ選択は任意であるが、採算性，操業性などの生産面並びに実用性，用途汎用性から総合的に判断すると、溶剤紡糸セルロース繊維「リヨセル」（レンチング社製）、「テンセル」（コートルズ社製）もしくは「マイクロモダール」（レンチング社製）又は綿のいずれか単独が望ましい。
【００１５】
本発明の吸湿発熱性セルロース系繊維は、既述したセルロース系繊維を付帯加工することで得られる。ただし、「リヨセル」，「テンセル」，「マイクロモダール」あるいは綿に代表されるセルロース繊維だけでかかるセルロース系繊維を構成することは、後に織編物にした際、吸水・吸湿性やソフト感，ふくらみ感をより向上させる効果を奏するが、セルロース繊維特有の欠点、すなわち家庭洗濯時の湿潤状態で摩擦を受けるとステープルが繊維軸方向に割繊しフィブリル化が発生しやすい他、シワも寄りやすく、縫製商品においては、織編物の伸縮率変動により縫い糸との間に物理的糸長差が生じ、パッカリングを誘発するなど仕立て映えに劣る面がある。したがってこれらの欠点をそのまま被ることになるため、白化防止加工や形態安定加工をあらかじめ施すのが望ましい。かかる加工方法は公知法に準じて行えばよく、設備，効率などを考慮して、紡績工程中あるいは織編物の準備工程に供すことができる糸条形態になった後に施すのが望ましい。一例を示すと、白化防止加工は、織編物に対し、エキソグルカナーゼ，エンドグルカナーゼ，セルビアーゼなどのセルロース分解酵素で処理した後、ポリウレタン樹脂含有水溶液に浸漬する。また形態安定加工は、撥水加工を施し、縫製商品とした後にホルムアルデヒドによる気相加工を施す。
【００１６】
このようにして得られたセルロース系繊維に対し、分子中に少なくとも２個のヒドラジド基を有するヒドラジン誘導体の水溶液を付与することで、該セルロース系繊維表面上へ該ヒドラジン誘導体を化学的に固着させて本発明の吸湿発熱性セルロース系繊維を得ることができる。吸湿発熱性は、繊維の水酸基に水分子が結合し、水和する際の水和熱により与えられる。かかるヒドラジン誘導体は、両末端にヒドラジド基を有しているため水和可能な官能基が多く、従来にない高い吸湿発熱効果を示す。
本発明において分子中に少なくとも２個のヒドラジド基を有するヒドラジン誘導体とは、例えばコハク酸ジヒドラジド，カルボジヒドラジド，アジピン酸ジヒドラジド，セバチン酸ジヒドラジド，ドデカン二酸ジヒドラジド，イソフタル酸ジヒドラジド，マレイン酸ジヒドラジド，ポリアクリル酸ヒドラジドなどの化合物であり、加工性・コストを勘案すればコハク酸ジヒドラジドを用いるのが望ましい。
【００１７】
本発明においては、洗濯耐久性を向上させるため、分子中に少なくとも２個の反応性官能基を有する化合物を介在させて、前記ヒドラジン誘導体をかかるセルロース系繊維表面上へ固着させるのが望ましい。これは、前記分子中に少なくとも２個の反応性官能基を有する化合物の１つの反応性官能基がセルロース分子の水酸基と化学結合し、かつもう１つの反応性官能基がヒドラジン誘導体のヒドラジド基と化学結合すれば、洗濯及び機械耐久性が向上する作用を奏するためである。
分子中に少なくとも２個の反応性官能基を有する化合物としては、エポキシ系樹脂、アミノプラスト樹脂、イソシアネート系樹脂などをあげることができる。
【００１８】
エポキシ樹脂とは、分子の末端にグリシジル基を有する化合物を指し、水溶性のものである。具体的にはソルビトールポリグリシジルエーテル，ソルビタンポリグリシジルエーテル，グリセロールポリグリシジルエーテル，ポリグリセロールポリグリシジルエーテル，ポリエチレングリコールジグリシジルエーテル，ポリプロピレングリコールジグリシジルエーテルなどが例示できる。
アミノプラスト樹脂とは、グリオキザール，メチル化トリメチロールメラミン，ジメチロールエチレン尿素，ジメチロールトリアゾン，メチル化ジメチロールウロン，ジメチロールプロピレン尿素，ジメチロールグリオキザールモノウレイン，テトラメチロールグリオキザールジウレインなどのＮ−メチロール系樹脂を指す。アミノプラスト樹脂には通常触媒が使用され、例えば、硝酸亜鉛のような酸の金属塩、ルイス酸，ブレンステッド酸などが用いられる。
さらに、イソシアネート系樹脂とは、分子の末端にイソシアネート基を有する化合物を指し、水溶性のものである。
【００１９】
他方、本発明の吸湿発熱性セルロース系繊維は、前記セルロース系繊維にシリコーン系化合物及び天然保湿成分を固着させることによっても得ることができる。これはシリコーン系化合物の発熱性と天然保湿成分の吸湿性が相乗効果をなすことで奏されるものである。シリコーン系化合物としては、「シリコーランＡＮ−１８００」（一方社油脂工業（株）製）、天然保湿成分としては、「タンドル」シリーズ（大和化学工業（株）製）が特に望ましく、この組合せの場合、洗濯耐久性も十分発現することができる。
【００２０】
また、より高い吸湿発熱性を得たい場合は、既述したヒドラジン誘導体および反応性官能基を有する化合物による処理、並びに前記シリコーン系化合物及び天然保水成分に
よる処理を併用すればよい。この場合２つの処理は別個に行うのが品質安定上望ましい。
【００２１】
次に、加工条件について言及する。
かかるヒドラジン誘導体は、繊維重量に対して０．５〜２０重量部固着するよう用いるのが望ましい。ヒドラジン誘導体が０．５重量部未満であると十分な吸湿発熱性が得られず、２０重量部を超えるとコスト高になり望ましくない。また、分子中に少なくとも２個の反応性官能基を有する化合物は、繊維重量に対して０．５〜３０重量部固着するよう用いるのが望ましい。反応性官能基を有する化合物が０．５重量部未満であると架橋が十分に進まず、３０重量部を超えるとヒドラジド基末端を封鎖する場合があり、望ましくない。
一方、かかるシリコーン系化合物は、繊維重量に対して０．５〜２０重量部固着するよう用いるのが望ましい。シリコーン系化合物が０．５重量部未満であると十分な発熱性が得られず、２０重量部を超えるとコスト高になり望ましくない。また、かかる天然保湿成分は繊維重量に対して０．５〜３０重量部固着するよう用いるのが望ましい。天然保水成分が０．５重量部未満であると十分な吸湿性が得られず、２０重量部を超えるとベトツキ感が発生しやすく望ましくない。
【００２２】
さらに、以上の加工には、柔軟剤やフィックス剤などの薬剤を併用してもよい。加工方法としては公知の方法で付与すればよいが、実用的にはパディング法が好ましい。絞り率は５０〜１１０％が望ましい。処理液の付与後、乾燥，熱処理を行う。乾燥は８０〜１８０℃で、好ましくは８０〜１３０℃で０．５〜５分間行い、熱処理は１１０〜２００℃で、好ましくは１１０〜１８０℃で０．５〜５分間行う。
【００２３】
次に、以上の如くして得られた吸湿発熱性セルロース系繊維を用いた織編物について言及する。
本発明の織編物は、かかる吸湿発熱性セルロース系繊維が構成糸の全部もしくは一部であればよい。したがって、目的に応じ他糸と合撚（交撚），混繊，交織，配列，交編など任意の形態で組み合わせることで、織編物を構成すればよい。他糸とは、ポリエステル，ポリアミド，アクリル，ポリウレタン，ポリオレフィンなどの合成繊維、トリアセテートなどの半合成繊維、ビスコースレーヨン，キュプラ，溶剤紡糸セルロース繊維などの再生繊維、綿，羊毛，絹，麻などの天然繊維を指し、長・短繊維いずれの形態でもよく、生糸，加工糸の区別は問わない。
一方、本発明の吸湿発熱性セルロース系繊維単独での撚糸や空気混繊、あるいは二本双糸，三本合撚糸などにした上で、織編物の製造に供しても何ら差し支えない。また組織・密度に関わる設計、並びに織編物となす際の準備及び製織編に関わる工程条件・機種は適宜選択することができる。具体的には織物の経糸準備は、ワーパー，サイジング，ビーミングを経る通常の工程が望ましく、撚糸または混繊による糸条を供する場合は部分整経でもよい。織機は風綿発生を考慮しレピア織機もしくはエアージェットルームが望ましい。編物の場合は、通常の機種で適宜条件設定すれば対応可能である。
【００２４】
本発明の織編物は、以上詳説した、糸条へ吸湿発熱性を付与した後に織編物とする以外に、後加工でかかる機能を付与してもよい。すなわち、構成糸の全部もしくは一部がセルロース系繊維である通常の染色加工上り織編物を用意し、既述した糸条への付帯加工と同様の原理で加工する。加工機は公知の機種にて対応可能で、糸条の場合と同様、パディング−絞り−乾燥−熱処理を経るのが望ましい。処理剤の固着量，乾燥及び熱処理温度などの加工条件は既述した糸条のそれと同じでよいが、処理液付与後の絞り率は、組織・密度の関係上、織物で５０〜１００％，編物で７０〜１２０％が望ましい。
【００２５】
さらに、本発明の織編物に、透湿防水性，制電性，撥水性など所要する第３の機能を付加する場合は、既述した本発明の織編物を得た後、改めてかかる加工を施せばよい。
【００２６】
【作用】
本発明では、分子中に少なくとも２個のヒドラジド基を有するヒドラジン誘導体の水溶液をセルロース系繊維に付与することで、該セルロース系繊維表面上へ該ヒドラジン誘導体を化学的に固着させて本発明の吸湿発熱性セルロース系繊維を得ることができる作用を奏す。吸湿発熱性は、繊維の水酸基に水分子が結合し、水和する際の水和熱により与えられ、かかるドラジン誘導体は、両末端にヒドラジド基を有しているため水和可能な官能基が多く、従来にない高い吸湿発熱効果を示す。
本発明においては、洗濯耐久性を向上させるため、分子中に少なくとも２個の反応性官能基を有する化合物を介在させて、前記ヒドラジン誘導体をかかるセルロース系繊維表面上へ固着させるのが望ましい。これは、前記分子中に少なくとも２個の反応性官能基を有する化合物の１つの反応性官能基がセルロース分子の水酸基と化学結合し、かつもう１つの反応性官能基がヒドラジン誘導体のヒドラジド基と化学結合すれば、耐久性が向上する作用を奏するためである。
さらに、本発明の吸湿発熱性セルロース系繊維は、前記セルロース系繊維にシリコーン系化合物及び天然保湿成分を固着させることによっても得ることができる。これはシリコーン系化合物の発熱性と天然保湿成分の吸湿性が相乗効果によって奏される作用である。
【００２７】
【実施例】
次に、本発明を実施例によってさらに具体的に説明する。
実施例における試料の吸湿発熱性能の測定評価は、加工上がり及び家庭洗濯（ＪＩＳ−Ｌ０２１７、１０３法）２０回後の試料について、下記の方法により評価した。
（吸湿発熱性）
測定試料と比較用試料をそれぞれ２枚重ねにした状態で１０ｃｍ×１０ｃｍの袋状に縫製する。試料を１０５℃で２時間絶乾した後、袋内に温度センサーを設置して、３０℃×４０％ＲＨの環境に４時間放置する。その後、３０℃×９０％ＲＨの環境に速やかに試料を移行させ、移行直後からの温度変化を２０分間記録、次式に準じ吸湿発熱性ΔＴｍａｘを算出する。
ΔＴｍａｘ＝Ｔ１−Ｔ２
ただし、ΔＴｍａｘ：吸湿発熱性Ｔ１：測定試料の最大温度（℃）Ｔ２：比較用試料（ブランク：吸湿発熱未加工布）の最大温度濃度
（洗濯耐久性）
ＪＩＳＬ−１０４７１０３法に準じて家庭洗濯を２０回行った後、吸湿発熱性を測定した。
【００２８】
実施例１
通常の方法で糊抜き・精練・漂白・染色された綿１００％の編物（２０／１フライス，目付け２７０ｇ／ｍ^２）をセルロース系編物として用意した。次に、下記処方１に示す処理液を上記セルロース系編物へ絞り率１００％でパディング法により付与した後、１００℃×１２０秒乾燥、続いて１７０℃×６０秒熱処理して本発明の吸湿発熱性セルロース系織物を得た。
（処方１）
コハク酸ジヒドラジド４％（日本ヒドラジン（株）製）
デナコールＥＸ−８３０４％（長瀬ケムテックス（株）製ポリエチレングリコールジグリシジルエーテル）
【００２９】
実施例２
通常の方法で糊抜き・精練・漂白・染色されたポリエステル／綿＝５０／５０の編物（２０／１フライス，目付け２４０ｇ／ｍ^２）をセルロース系編物として用意した。次に、下記処方２に示す処理液を上記セルロース系編物へ絞り率１００％でパディング法により付与した後、１００℃×１２０秒乾燥、続いて１７０℃×６０秒熱処理して本発明の吸湿発熱性セルロース系編物を得た。
（処方２）
コハク酸ジヒドラジド４％（日本ヒドラジン（株）製）
スミテックスレジンＮＳ−１９８％（住友化学（株）製変性グリオキザール系樹脂）
スミテックスアクセラレーターＡＣＸ２．４％（住友化学（株）製有機アミン系触媒）
【００３０】
実施例３
通常の方法で糊抜き・精練・漂白・染色された綿１００％の編物（２０／１フライス，目付け２７０ｇ／ｍ^２）をセルロース系編物として用意した。次に、下記処方３に示す処理液を上記セルロース系編物へ絞り率１００％でパディング法により付与した後、１００℃×１２０秒乾燥、続いて１７０℃×６０秒熱処理して本発明の吸湿発熱性セルロース系織物を得た。
（処方３）
シリコーランＡＮ−１８００４％（一方社油脂工業（株）製シリコーン樹脂）
タンドルＤＣ−１００４％（大和化学工業（株）製天然保湿成分）
【００３１】
本発明の吸湿発熱性を測定し、その結果を表１に示す。
【表１】

【００３２】
【発明の効果】
本発明の吸湿発熱性セルロース系繊維は、優れた吸湿発熱性を具備し、洗濯耐久性にも優れ、加えて既存設備を用いて容易に製造でき、かつ低コストで製造できる効果を奏する。
また、本発明の織編物は用途汎用性に優れ、アウター用途はもとよりインナー・小物への展開も図れ、本発明の織編物に第３の機能を具備させれば多岐に渡る用途展開が可能となる。特に処理剤にシリコーン系化合物及び天然保湿成分を用いると、肌にもやさしくタイツ，下着，スカート，ブラウスなど市場規模の大きい高い婦人向けに好適に対応できる効果を奏する。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a moisture-absorbing and heat-generating cellulosic fiber having a function of absorbing moisture and generating heat, and a woven or knitted fabric.
[0002]
[Prior art]
Conventionally, far-infrared radiating materials and thermal storage materials have been developed as autumn-winter warm clothing, and are widely used particularly in the field of sports and outdoors, for example, winter clothing such as ski wear, windbreakers, and blousons. Although these materials have excellent heat retention function, they are mainly used only for outer applications due to the problem that their functions deteriorate in places where sunlight does not shine, and they are used for inner applications such as preventing cold feeling due to sweating during exercise He remained with potential needs.
In order to solve this problem, a moisture-absorbing heat-generating material that generates heat energy when absorbing moisture from the body or the outside air has been developed, which not only exhibits excellent heat retention function regardless of the external environment, but also has It has also become possible to expand into inner uses, which has been eagerly desired by consumers who are worried.
[0003]
Examples of the moisture-absorbing heat-generating material include a woven or knitted fabric produced using an acrylate fiber yarn obtained by strongly cross-linking a chemically modified product having a hydrophilic group at a high density as an example of a yarn having the function (for example, see Patent Document 1). Also, as an example of imparting the function by post-processing, N-methylol (meth) acrylamide (N-MAM) is bonded to the hydroxyl group of the cellulose molecule in a woven or knitted fabric containing cellulose fiber as one component, and then N- A method of polymerizing a polymerizable vinyl compound starting from the vinyl group of MAM (for example, see Patent Document 2), or reacting a polycarboxylic acid having at least three carboxyl groups in a molecule with a cellulosic woven or knitted fabric, A method of soaping with an aqueous solution of a metal salt (for example, see Patent Document 3) has been proposed.
[0004]
These moisture-absorbing heat-generating materials all absorb moisture such as sweat generated from the body and moisture such as dew condensation caused by changes in the external environment, and convert them into heat energy. It retains its original function and texture, and can be applied not only to outer uses but also to accessories such as inners, socks, hair bands, and hats.
However, the method of manufacturing any of the moisture-absorbing heat-generating materials is complicated, and the problem of high cost remains. The invention according to the above-mentioned Patent Document 1 has such a function only when the acrylate fiber molecule is crosslinked at a high density and strongly with a chemically modified product having a hydrophilic group. Since the yarn is slightly colored by the body, there is an inherent problem that color fluctuation of the dyeing is likely to occur.
Further, in the invention according to Patent Document 2, since a polymer that forms the basis of such a function is formed on a woven or knitted fabric during processing, the conditions are severe and the performance tends to vary.
On the other hand, the invention according to the above-mentioned Patent Document 3 has a problem of high cost, though the condition is not severe, but it is necessary to go through two treatment steps of treating with a polycarboxylic acid and then soaping with an aqueous solution of an alkali metal salt. ing.
[0005]
[Patent Document 1]
Japanese Patent Publication No. 7-59762 ([0015] and [0017])
[Patent Document 2]
Japanese Patent No. 2898623 (Claims 6 and [0008])
[Patent Document 3]
JP-A-2000-256962 (Claim 1)
[0006]
[Problems to be solved by the invention]
The present invention solves such a problem, and has excellent moisture absorption and heat generation by applying a hydrazine derivative having at least two hydrazide groups in a molecule, a silicone compound and a natural moisturizing component, and An object of the present invention is to provide a moisture-absorbing and heat-generating cellulosic fiber which is excellent in washing durability, easy to process, and can be produced at low cost.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and focused on the hygroscopicity of hydrazine compounds. At least one hydrazide group of a compound having at least two or more hydrazide groups in a molecule has a hydroxyl group of a cellulose molecule. Or a compound having at least two reactive functional groups in a molecule, wherein one reactive functional group is chemically bonded to a hydroxyl group of a cellulose molecule, and another reactive functional group is a hydrazide of a hydrazine compound. The present inventors have found that, by chemically bonding to a group, or fixing a silicone compound and a natural moisturizing component on fibers, it is possible to impart moisture-absorbing heat generation with excellent washing durability to cellulosic fibers and cellulosic woven or knitted fabrics, and reached the present invention.
That is, the present invention provides the following (1) to (13).
[0008]
(1) A moisture-absorbing and heat-generating cellulosic fiber, wherein a hydrazine derivative having at least two hydrazide groups in a molecule is fixed.
(2) The hygroscopic heat-generating cellulosic fiber according to (1), wherein the hydrazine derivative is fixed in an amount of 0.5 to 20 parts by weight based on the weight of the cellulosic fiber as a base material.
Further, preferred embodiments include the following.
(3) The method according to (1) or (2), wherein the hydrazine derivative is fixed to a cellulosic fiber as a base material via a compound having at least two reactive functional groups in a molecule. Moisture absorbing and exothermic cellulosic fibers.
(4) The heat generated by moisture absorption according to (3), wherein the compound having at least two reactive functional groups is composed of a component containing at least one of an epoxy resin, an aminoplast resin and an isocyanate resin. Cellulosic fibers.
(5) A moisture-absorbing and heat-generating cellulosic fiber comprising a silicone compound and a natural moisturizing component fixed thereto.
(6) The moisture-absorbing and heat-generating cellulosic fiber according to (4), wherein the silicone-based compound and the natural moisturizing component are coated.
(7) A woven or knitted fabric characterized by using the moisture-absorbing and heat-generating cellulosic fiber according to any one of (1) to (6) as at least a part of a constituent yarn.
[0009]
On the other hand, the following is included as an embodiment in which post-processing is performed using a known cellulosic woven or knitted fabric to impart moisture absorption and heat generation.
(8) A moisture-absorbing and heat-generating cellulose-based woven or knitted fabric comprising a cellulose fiber at least as a part of a constituent yarn, wherein the hydrazine derivative is fixed throughout the woven or knitted fabric.
(9) The moisture-absorbing and heat-generating cellulose-based woven or knitted fabric according to (8), wherein the hydrazine derivative is fixed in an amount of 0.5 to 20 parts by weight based on the weight of the cellulose-based woven or knitted fabric as a base material.
(10) A woven or knitted fabric containing at least a part of the constituent yarns of the cellulosic fiber, wherein the hydrazine derivative is formed through a compound having at least two reactive functional groups in the molecule throughout the woven or knitted fabric. A moisture-absorbing and heat-generating cellulosic woven or knitted fabric characterized by being fixedly attached.
(11) The heat generated by moisture absorption according to (10), wherein the compound having at least two reactive functional groups is composed of a component containing at least one of an epoxy resin, an aminoplast resin and an isocyanate resin. Cellulosic woven or knitted fabric.
(12) A woven or knitted fabric containing at least a part of the constituent yarns of the cellulosic fiber, wherein the silicone compound and the natural moisturizing component are fixed throughout the woven or knitted fabric. Cellulosic woven or knitted fabric.
(13) The moisture-absorbing and heat-generating cellulose-based woven or knitted fabric according to claim 11, wherein the silicone-based compound and the natural moisturizing component are coated.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The moisture-absorbing and heat-generating cellulosic fiber of the present invention is obtained by subjecting the cellulosic fiber to additional treatment. Such cellulosic fibers refer to fiber yarns containing cellulose fibers as a main component. Cellulose fibers include, for example, cotton and hemp in the case of natural fibers, and viscose rayon, cupra, and solvent-spun cellulose fibers in the case of regenerated fibers. The fiber form may be either long or short fiber, and the fineness and fiber length are not particularly limited.
[0011]
Depending on the purpose of the cellulosic fiber used in the present invention, these fibers may be used alone or in combination, or a mixture of one or more fibers selected from the cellulose fibers and one or more other yarns may be used. Other yarns to be mixed include, for example, natural fibers such as wool and silk, synthetic fibers such as polyester, polyamide, acrylic, polyurethane, and polyolefin, and semi-synthetic fibers such as triacetate. Short fibers may be used, and fineness and fiber length are not particularly limited.
[0012]
The mixing method and mixing ratio are not particularly limited, and when the fibers to be mixed are composed of only short fibers, if the fibers are provided as a blended yarn, for example, the respective fibers are blended in a blended cotton process, and a card, a drawing, a roving, After spinning, spinning each fiber to the carding process and then combining it with a sliver in the drawing process, or roving / spinning by slivering multiple slivers with each fiber drawn independently There are spinning methods. When it is desired to improve the design, a fiber having a gloss or a fiber already dyed is used. For example, by mixing an appropriate amount of original yarn or pre-dyed yarn produced by mixing a colorant during fiber production, or fibers of different cross-section yarns with different gloss or different matting agents, the gloss and hue after dyeing You can express different heather feeling.
On the other hand, if provided as a composite yarn, a method of preparing a sliver of the yarn constituting the composite yarn according to a known method and compounding in a roving step, or preparing a roving yarn of the yarn constituting the composite yarn and refining the sliver A method of compounding in the spinning step is given. In any method, a core-sheath structure yarn can be obtained by providing a feed difference between yarns, and a twisted yarn can be obtained if no feed difference is provided.
[0013]
When the fibers to be mixed are composed of long fibers and short fibers, a long fiber yarn and a short fiber roving prepared by a known method are prepared, respectively, and are manufactured through a spinning process. In this method, similarly to the above, a core-sheath structure yarn can be obtained by providing a feed difference between the yarns, and if no feed difference is provided, a twisted yarn can be obtained.
On the other hand, when the fibers to be mixed are composed of only long fibers, the respective yarns are aligned in a parn winder, air-blended, or mixed in a form twisted by a twisting machine. Is raised.
[0014]
As described above, the cellulosic fiber used in the present invention can be selected arbitrarily according to the purpose. However, when comprehensively judged from the aspects of production, such as profitability and operability, as well as practicality and versatility in use, the solvent-spun cellulose fiber “ Any of Lyocell (manufactured by Lenting), Tencel (manufactured by Coatles) or "Micromodal" (manufactured by Lenteng) or cotton is preferred.
[0015]
The moisture-absorbing and heat-generating cellulosic fiber of the present invention can be obtained by subjecting the above-mentioned cellulosic fiber to additional processing. However, the construction of such cellulosic fibers using only cellulosic fibers such as "Lyocell", "Tencel", "Micromodal", or cotton is not possible when the fabric is woven or knitted later, as it absorbs and absorbs moisture, has a soft feel, and swells. Although it has the effect of further improving the feeling, the disadvantages unique to cellulose fibers, namely that when staples are rubbed in the wet state at home washing, the staples split in the fiber axis direction and fibrillation is easy to occur, wrinkles are also easy to wrinkle, In a sewn product, a physical thread length difference is generated between the woven and knitted fabric and a sewing thread due to a change in the expansion / contraction ratio of the woven or knitted fabric, and the tailoring appearance is inferior, such as inducing puckering. Therefore, since these disadvantages are directly affected, it is desirable to perform a whitening prevention process or a form stabilization process in advance. Such a processing method may be performed according to a known method, and is preferably performed during the spinning process or after the yarn has been formed into a thread form that can be used for the preparation process of the woven or knitted fabric, in consideration of equipment, efficiency, and the like. As an example, in the whitening prevention treatment, the woven or knitted fabric is treated with a cellulose-decomposing enzyme such as exoglucanase, endoglucanase, or serbiase, and then immersed in a polyurethane resin-containing aqueous solution. In the form stabilization processing, a water-repellent processing is performed, and a vapor-phase processing with formaldehyde is performed after a sewn product is obtained.
[0016]
By applying an aqueous solution of a hydrazine derivative having at least two hydrazide groups in the molecule to the cellulosic fiber thus obtained, the hydrazine derivative is chemically fixed on the surface of the cellulosic fiber. Thus, the heat-absorbing and heat-generating cellulosic fiber of the present invention can be obtained. The hygroscopic heat generation is given by the heat of hydration when water molecules bind to the hydroxyl groups of the fiber and hydrate. Such a hydrazine derivative has a hydrazide group at both ends and therefore has many hydratable functional groups and exhibits an unprecedentedly high heat absorption and heat generation effect.
In the present invention, the hydrazine derivative having at least two hydrazide groups in the molecule includes, for example, succinic dihydrazide, carbodihydrazide, adipic dihydrazide, sebacic dihydrazide, dodecane diacid dihydrazide, isophthalic dihydrazide, maleic dihydrazide, polyacrylic acid It is a compound such as acid hydrazide, and it is desirable to use succinic dihydrazide in consideration of processability and cost.
[0017]
In the present invention, in order to improve the washing durability, it is desirable that the hydrazine derivative is fixed on the surface of the cellulosic fiber by interposing a compound having at least two reactive functional groups in the molecule. This is because one reactive functional group of the compound having at least two reactive functional groups in the molecule is chemically bonded to a hydroxyl group of a cellulose molecule, and another reactive functional group is bonded to a hydrazide group of a hydrazine derivative. This is because the chemical bonding provides an effect of improving the washing and machine durability.
Examples of the compound having at least two reactive functional groups in a molecule include an epoxy resin, an aminoplast resin, and an isocyanate resin.
[0018]
The epoxy resin refers to a compound having a glycidyl group at the terminal of the molecule, and is a water-soluble one. Specific examples include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
Aminoplast resins include N such as glyoxal, methylated trimethylol melamine, dimethylol ethylene urea, dimethylol triazone, methylated dimethylol uron, dimethylol propylene urea, dimethylol glyoxal monourein, and tetramethylol glyoxal diurein. -Refers to a methylol-based resin. A catalyst is usually used for the aminoplast resin, and for example, metal salts of acids such as zinc nitrate, Lewis acids, Bronsted acids and the like are used.
Further, the isocyanate-based resin refers to a compound having an isocyanate group at a terminal of a molecule, and is a water-soluble resin.
[0019]
On the other hand, the moisture-absorbing and heat-generating cellulosic fiber of the present invention can also be obtained by fixing a silicone compound and a natural moisturizing component to the cellulosic fiber. This is achieved by the synergistic effect of the heat build-up of the silicone compound and the hygroscopicity of the natural moisturizing component. As the silicone compound, “Silicoran AN-1800” (manufactured by Yushi Yushi Kogyo Co., Ltd.) is particularly preferable, and as the natural moisturizing component, the “Tundle” series (manufactured by Daiwa Chemical Industry Co., Ltd.) is particularly desirable. In addition, washing durability can be sufficiently exhibited.
[0020]
When it is desired to obtain higher moisture absorption and heat generation, the treatment with the hydrazine derivative and the compound having a reactive functional group as described above, and the treatment with the silicone compound and the natural water retaining component may be used in combination. In this case, it is desirable to perform the two processes separately for quality stability.
[0021]
Next, processing conditions will be described.
Such a hydrazine derivative is desirably used so as to be fixed at 0.5 to 20 parts by weight based on the weight of the fiber. If the amount of the hydrazine derivative is less than 0.5 part by weight, sufficient heat generation by moisture absorption cannot be obtained. If the amount of the hydrazine derivative exceeds 20 parts by weight, the cost increases, which is not desirable. The compound having at least two reactive functional groups in the molecule is desirably used so as to be fixed at 0.5 to 30 parts by weight based on the weight of the fiber. If the amount of the compound having a reactive functional group is less than 0.5 parts by weight, crosslinking does not proceed sufficiently, and if it exceeds 30 parts by weight, the terminal of the hydrazide group may be blocked, which is not desirable.
On the other hand, it is desirable to use the silicone compound so as to be fixed at 0.5 to 20 parts by weight with respect to the weight of the fiber. If the amount of the silicone compound is less than 0.5 part by weight, sufficient heat build-up cannot be obtained, and if the amount exceeds 20 parts by weight, the cost increases, which is not desirable. Further, it is desirable to use such a natural moisturizing component so as to be fixed at 0.5 to 30 parts by weight based on the weight of the fiber. If the natural water-retaining component is less than 0.5 part by weight, sufficient hygroscopicity cannot be obtained, and if it exceeds 20 parts by weight, a sticky feeling is apt to occur, which is not desirable.
[0022]
Further, agents such as a softening agent and a fixing agent may be used in combination for the above processing. As a processing method, a known method may be used, but a padding method is preferable for practical use. The aperture ratio is desirably 50 to 110%. After applying the treatment liquid, drying and heat treatment are performed. Drying is performed at 80 to 180 ° C, preferably at 80 to 130 ° C for 0.5 to 5 minutes, and heat treatment is performed at 110 to 200 ° C, preferably at 110 to 180 ° C for 0.5 to 5 minutes.
[0023]
Next, the woven or knitted fabric using the moisture-absorbing and heat-generating cellulosic fibers obtained as described above will be described.
In the woven or knitted fabric of the present invention, the moisture-absorbing and heat-generating cellulosic fibers may be all or part of the constituent yarns. Therefore, a woven or knitted material may be formed by combining with other yarns in any form such as ply twist (twisting), mixed fiber, cross weaving, arrangement, and cross knitting according to the purpose. Other yarns include synthetic fibers such as polyester, polyamide, acrylic, polyurethane, and polyolefin; semi-synthetic fibers such as triacetate; regenerated fibers such as viscose rayon, cupra, and solvent-spun cellulose fibers; and cotton, wool, silk, and hemp. It refers to natural fibers, and may be in the form of either long or short fibers.
On the other hand, the yarn of the present invention may be formed into a twisted yarn or air-mixed fiber using only the moisture-absorbing heat-generating cellulosic fiber, or a double-twisted yarn, a triple-twisted yarn, or the like, and then used in the production of a woven or knitted fabric. In addition, the design relating to the structure / density, and the preparation conditions for forming a woven or knitted product and the process conditions / models relating to the weaving / knitting can be appropriately selected. Specifically, the preparation of the warp of the woven fabric is desirably a normal process of passing through a warper, a sizing, and a beaming, and may be a partial warping when providing a yarn by twisting or blending. As for the loom, a rapier loom or an air jet loom is preferable in consideration of the generation of fly wool. In the case of a knitted fabric, it can be handled by appropriately setting conditions with a normal model.
[0024]
The woven or knitted fabric of the present invention may be provided with such a function by post-processing, in addition to the woven or knitted fabric after imparting the moisture-absorbing heat generation property to the yarn as described in detail above. That is, an ordinary dyed up-woven or knitted fabric in which all or a part of the constituent yarn is a cellulosic fiber is prepared, and is processed according to the same principle as that of the above-described supplementary processing to the yarn. A processing machine can be used with a known model, and it is preferable that padding-drawing-drying-heat treatment be performed as in the case of yarn. The processing conditions such as the fixing amount of the treatment agent, the drying and heat treatment temperatures may be the same as those of the yarn described above, but the drawing ratio after application of the treatment liquid is 50 to 100% for the woven fabric due to the structure / density. It is preferably 70 to 120% for a knitted fabric.
[0025]
Further, when the woven or knitted fabric of the present invention is provided with the required third function such as moisture permeability, antistatic property, or water repellency, after the woven or knitted fabric of the present invention described above is obtained, such processing is performed again. It should be applied.
[0026]
[Action]
In the present invention, an aqueous solution of a hydrazine derivative having at least two hydrazide groups in a molecule is applied to the cellulose-based fiber, whereby the hydrazine derivative is chemically fixed on the surface of the cellulose-based fiber, and the moisture absorption of the present invention is improved. It has the effect of obtaining exothermic cellulosic fibers. Hygroscopic heat generation is given by the heat of hydration when a water molecule binds to the hydroxyl group of the fiber and hydrates, and such a hydrazine derivative has a hydrazide group at both terminals, so that a hydratable functional group is provided. In many cases, it exhibits a high moisture absorption and heat generation effect that has never been seen before.
In the present invention, in order to improve the washing durability, it is desirable that the hydrazine derivative is fixed on the surface of the cellulosic fiber by interposing a compound having at least two reactive functional groups in the molecule. This is because one reactive functional group of the compound having at least two reactive functional groups in the molecule is chemically bonded to a hydroxyl group of a cellulose molecule, and another reactive functional group is bonded to a hydrazide group of a hydrazine derivative. This is because the chemical bonding provides an effect of improving the durability.
Furthermore, the moisture-absorbing and heat-generating cellulosic fiber of the present invention can also be obtained by fixing a silicone compound and a natural moisturizing component to the cellulosic fiber. This is an effect in which the exothermicity of the silicone compound and the hygroscopicity of the natural moisturizing component are exerted by a synergistic effect.
[0027]
【Example】
Next, the present invention will be described more specifically with reference to examples.
The measurement and evaluation of the moisture absorption and heat generation performance of the samples in the examples were evaluated by the following methods for the samples after finishing the processing and 20 times after home washing (JIS-L0217, 103 method).
(Hygroscopic heat generation)
The measurement sample and the comparison sample are sewn in a bag shape of 10 cm × 10 cm in a state where two sheets are stacked. After the sample was absolutely dried at 105 ° C. for 2 hours, a temperature sensor was set in the bag and left in an environment of 30 ° C. × 40% RH for 4 hours. Thereafter, the sample is immediately transferred to an environment of 30 ° C. × 90% RH, the temperature change immediately after the transfer is recorded for 20 minutes, and the moisture absorption heat generation ΔTmax is calculated according to the following equation.
ΔTmax = T1-T2
Here, ΔTmax: heat absorption and heat generation T1: maximum temperature of the measurement sample (° C.) T2: maximum temperature concentration of the comparative sample (blank: unprocessed cloth with heat absorption) (washing durability)
After home washing was performed 20 times in accordance with JIS L-1047 103 method, the heat of moisture absorption was measured.
[0028]
Example 1
A 100% cotton knitted fabric (20/1 milling, basis weight 270 g / m ² ) that had been desizing, scouring, bleaching, and dyeing by an ordinary method was prepared as a cellulosic knitted fabric. Next, the treatment liquid shown in the following formula 1 was applied to the above-mentioned cellulose-based knitted fabric at a squeezing ratio of 100% by a padding method, and then dried at 100 ° C. for 120 seconds, and then heat-treated at 170 ° C. for 60 seconds to generate moisture absorption heat of the present invention. A cellulose-based woven fabric was obtained.
(Prescription 1)
Succinic dihydrazide 4% (manufactured by Nippon Hydrazine Co., Ltd.)
Denacol EX-830 4% (Polyethylene glycol diglycidyl ether manufactured by Nagase ChemteX Corporation)
[0029]
Example 2
Polyester / cotton = 50/50 knitted fabric (20/1 milling, basis weight 240 g / m ² ) which had been desizing, scouring, bleaching and dyeing by a usual method was prepared as a cellulose-based knitted fabric. Next, the treatment liquid shown in the following formula 2 is applied to the above-mentioned cellulose-based knitted fabric by a padding method at a squeezing ratio of 100%, and then dried at 100 ° C. for 120 seconds, and then heat-treated at 170 ° C. for 60 seconds to generate moisture absorption heat of the present invention. A cellulose-based knitted fabric was obtained.
(Prescription 2)
Succinic dihydrazide 4% (manufactured by Nippon Hydrazine Co., Ltd.)
Sumitec Resin NS-19 8% (Modified glyoxal resin manufactured by Sumitomo Chemical Co., Ltd.)
Sumitex accelerator ACX 2.4% (organic amine catalyst manufactured by Sumitomo Chemical Co., Ltd.)
[0030]
Example 3
A 100% cotton knitted fabric (20/1 milling, basis weight 270 g / m ² ) that had been desizing, scouring, bleaching, and dyeing by an ordinary method was prepared as a cellulosic knitted fabric. Next, the treatment liquid shown in Formulation 3 below was applied to the above-mentioned cellulosic knitted fabric by a padding method at a squeezing ratio of 100%, followed by drying at 100 ° C. for 120 seconds, followed by heat treatment at 170 ° C. for 60 seconds to produce the moisture absorption heat of the present invention. A cellulose-based woven fabric was obtained.
(Prescription 3)
4% Silicoran AN-1800 (silicone resin manufactured by YAS Co., Ltd.)
Tundle DC-100 4% (Natural moisturizing component manufactured by Daiwa Chemical Industry Co., Ltd.)
[0031]
The moisture absorption exothermicity of the present invention was measured, and the results are shown in Table 1.
[Table 1]

[0032]
【The invention's effect】
Effects of the Invention The moisture-absorbing and heat-generating cellulosic fiber of the present invention has excellent moisture-absorbing and heat-generating properties, is excellent in washing durability, and can be easily manufactured using existing equipment and has an effect of being manufactured at low cost.
In addition, the woven or knitted fabric of the present invention has excellent versatility in use, and can be developed not only for outer use but also for inner and small articles. If the woven and knitted fabric of the present invention is provided with the third function, it can be used in a wide variety of applications. Become. In particular, when a silicone-based compound and a natural moisturizing component are used as the treating agent, it has an effect of being gentle on the skin and suitable for women with a large market such as tights, underwear, skirts and blouses.

Claims

A hydrazine derivative having at least two hydrazide groups in a molecule is fixed thereon.

2. The moisture-absorbing and heat-generating cellulosic fiber according to claim 1, wherein the hydrazine derivative is fixed in an amount of 0.5 to 20 parts by weight based on the weight of the cellulosic fiber as a base material.

3. The heat-absorbing hygroscopic cellulose according to claim 1, wherein the hydrazine derivative is fixed to a cellulosic fiber as a base material via a compound having at least two reactive functional groups in a molecule. System fiber.

4. The moisture-absorbing and exothermic cellulose-based material according to claim 3, wherein the compound having at least two reactive functional groups is composed of a component containing at least one of an epoxy resin, an aminoplast resin and an isocyanate resin. fiber.

A moisture-absorbing and heat-generating cellulosic fiber comprising a silicone compound and a natural moisturizing component fixed thereto.

The moisture-absorbing and heat-generating cellulosic fiber according to claim 4, wherein the silicone-based compound and the natural moisturizing component are coated.

A woven or knitted fabric comprising the moisture-absorbing and heat-generating cellulosic fiber according to any one of claims 1 to 6 as at least a part of a constituent yarn.

What is claimed is: 1. A moisture-absorbing and heat-generating cellulose-based woven or knitted fabric comprising a cellulose fiber at least as a part of a constituent yarn, wherein the hydrazine derivative is fixed throughout the woven or knitted fabric.

9. The moisture-absorbing and heat-generating cellulose-based woven or knitted fabric according to claim 8, wherein the hydrazine derivative is fixed in an amount of 0.5 to 20 parts by weight based on the weight of the base material.

A woven or knitted fabric having at least a part of the constituent yarns composed of cellulosic fibers, wherein the hydrazine derivative is fixed throughout the woven or knitted fabric via a compound having at least two reactive functional groups in the molecule. And a moisture-absorbing and heat-generating cellulosic woven or knitted fabric.

11. The moisture-absorbing and exothermic cellulose-based material according to claim 10, wherein the compound having at least two reactive functional groups is composed of a component containing at least one of an epoxy resin, an aminoplast resin and an isocyanate resin. Weaving and knitting.

What is claimed is: 1. A woven / knitted fabric comprising a cellulose-based fiber at least as a part of a constituent yarn, wherein the silicone-based compound and the natural moisturizing component are fixed throughout the woven / knitted fabric. knitting.

The moisture-absorbing and heat-generating cellulose-based woven / knitted fabric according to claim 11, wherein the silicone-based compound and the natural moisturizing component are coated.