JP3849112B2 - A shrink-proofing agent and a shrink-proofing method for animal hair fiber products and animal leather products. - Google Patents

Description

【００２８】
表１において、硬度はＪＩＳ−Ｋ−７２１５に規定するＤデュロメーターを用いて測定した。また１００％モジュラスおよび伸長率は、０．３mmの膜を作製し、温度２３℃にて測定した。測定方法は、ＪＩＳ−Ｋ−６３０１に準拠した。
【００２９】
かかる水溶性ポリウレタンまたは水分散性ポリウレタンの好ましい配合量は５〜９４．７重量％、より好ましくは１０〜７０重量％、さらに好ましくは１５〜６０重量％である。その配合量が多くなると、本発明の処理剤で処理後の繊維を繰り返し水処理や水洗濯を行っても収縮を防止する。その量が９４．７重量％を超えて多くなると獣毛製品等の風合いが変化するので好ましくない。また５重量％未満では寸法の安定性が現れない。これらの水溶性ポリウレタンまたは水分散性ポリウレタンは二種以上を併用することができる。
【００３０】
Ｄ成分の２〜４価金属塩としては、無機酸もしくは有機酸の金属塩であり、好ましくは３〜４価の金属塩、より好ましくは３価の金属塩である。具体的には銅塩、亜鉛塩、カルシウム塩、マグネシウム塩、等の２価の金属塩や、アルミニウム塩、クロム塩、鉄塩、ランタン塩、セリウム塩、等の３価金属塩や、ジルコニウム塩、硅素塩、等の４価金属塩を挙げることができる。アルミニウム塩としては、アルミン酸ナトリウム、硫酸アルミニウム、硫酸アルミニウムアンモニウム、硝酸アルミニウム、酢酸アルミニウム、弗化アルミニウム、塩化アルミニウム、蓚酸アルミニウム、乳酸アルミニウム等、ジルコニウム塩としては硫酸ジルコニウムなどを例示できる。中でも硫酸アルミニウムが好適であり、他の金属塩との併用もまた好適である。
【００３１】
Ｅ成分の界面活性剤（ただしアルキル基の炭素数６以上の含窒素型界面活性剤を除く）はノニオン系界面活性剤が好ましく、またノニオン系界面活性剤とアニオン系界面活性剤の併用、またはノニオン系界面活性剤とカチオン系界面活性剤の併用が好ましく、両性界面活性剤も使用される。
【００３２】
ノニオン系界面活性剤としては、アルキルフェノールのエチレンオキシド付加物が好ましい。平均炭素数６〜１２アルキル基を有し、１〜２０モルのエチレンオキサイドを付加したポリオキシエチレンポリオキシプロピレンアルキルフェニールエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、アルキル基の炭素数６未満の脂肪酸（モノ）ジアルキルアミドまたはアルキルアミン、植物脂肪酸エステル、アルキルサッカロイド、脂肪酸グリセリンモノエステル、平均炭素数１０〜２０のアルキル基またはアルケニル基を有し、１〜２０モルエチレンオキサイドを付加したポリオキシエチレンアルキルまたはアルケニルエーテル、等を例示できる。
【００３３】
またアニオン性界面活性剤としては、下記のものを挙げることができる。
（１）高級脂肪酸のアルカリ金属塩（石鹸）
（２）平均炭素数１０〜２０の直鎖または分岐鎖のアルキル基またはアルケニル基を有し、１分子内に平均０．５〜８モルのエチレンオキサイドを付加したアルキル基またはアルケニル硫酸塩
（３）平均炭素数１０〜１６のアルキル基を有するアルキルベンゼンスルホン酸塩
（４）平均炭素数１０〜２０のアルキル基またはアルケニル基を有するアルキルまたはアルケニル硫酸塩
（５）平均１０〜２０の炭素原子を１分子内に有するオレフィンスルフォン酸塩（６）平均１０〜２０の炭素原子を１分子中に有するアルカンスルフォン酸塩
（７）スルホサクネートナトリウム塩
（８）エーテルカルボン酸塩
（９）高級アルコールのエトキシレート
（１０）高級アルコールのサルフェート
（１１）モノアルキルホスフェート
（１２）アルキルポリグリコシド
等を例示できる。
【００３４】
カチオン性界面活性剤としては
（１）脂肪族１級、２級、３級アミン塩および脂肪族４級アンモニウム
（２）芳香族４級アンモニウム塩
（３）複素環４級アンモニウム塩
（４）塩化ベンゼトニウム
（５）ピリヂニウム塩
（６）イミダゾリニウム塩
等を例示できる。
【００３５】
また両性界面活性剤としては
（１）アルキルベタイン型
（２）アミドベタイン型
等である。
【００３６】
上記のノニオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤および両性界面活性剤の各々は、２種以上を併用しても良い。
【００３７】
Ｆ成分のアルキル基の炭素数６以上の含窒素型界面活性剤としては、ヤシ油脂肪酸ジエタノールアミド、ポリオキシエチレンヤシ油脂肪酸モノエタノールアミド、ラウリン酸ジエタノールアミド、ヤシ油脂肪酸モノエタノールアミド、ステアリル酸モノ（ジ）エタノールアミド、ラウリン酸イソプロパノールアミド、ポリオキシエチレンアルキルアミン、アルキルアミノオキサイド等を例示できる。中でも水溶性のラウリン酸ジエタールアミド、ヤシ油脂肪酸ジエタノールアミド等のノニオン系界面活性剤が好ましい。
【００３８】
Ｆ成分のアルキル基の炭素数６以上の含窒素型界面活性剤としては、エチル硫酸ラノリン脂肪酸アミノプロルエチルジメチルアンモニウム、塩化ジステアリルメチルアンモニウム、塩化ステアリルジメチルベンジルアンモニウム、塩化アルキルトリメチルアンモニウム、塩化ステアリルトリメチルアンモニウム、塩化セチルトリメチルアンモニウム、塩化ベンザルコニウム（Ｒは主にラウリル基）、等の第４級アンモニウム塩型カチオン界面活性剤等を例示できる。
【００３９】
またＦ成分のアルキル基の炭素数６以上の含窒素型界面活性剤としては、ヤシ油脂肪酸アミドプロピルベタイン、ラウリン酸アミドプロピルベタイン、ラウリルジメチルアミノ酢酸ベタイン、２−アルキル−Ｎ−カルボキシル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン、Ｎ−ラウロイル−Ｎ’ヒドロキシエチルエチレンジアミンナトリウム、β−ラウリルアミノプロピオン酸ナトリウム等の両性界面活性剤等を例示できる。
【００４０】
Ｆ成分としては、上記のポリアミド系カチオン界面活性剤、非イオン・カチオン界面活性剤、非イオン界面活性剤、第４級アンモニウム塩型カチオン界面活性剤、両性界面活性剤等を例示できる。これらの界面活性剤の種類を変えることによって、処理後の防縮性、風合い（柔軟性、毛羽立ち性、ぬめり性、手触り性等）に変化を与えることができる。なかでもヤシ油脂肪酸、ラノリン脂肪酸等の天然脂肪酸をアルキル基に有する含窒素型界面活性剤が望ましい。これらの界面活性剤は二種以上を併用してもよい。
【００４１】
Ｇ成分の脂肪族アルデヒド化合物としては、アセトアルデヒド、パラアセトアルデヒド、メタアセトアルデヒド、ブチルアルデヒド、ヒドロキシブチルアルデヒド、グルタルアルデヒド、クロトンアルデヒド、マーガルアルデヒド、等を例示できる。
【００４２】
Ｇ成分の芳香族アルデヒド化合物としては、ベンズアルデヒド、ヒドロキシベンズアルデヒド、フォルムアルデヒド、桂皮アルデヒド、等を例示できる。
【００４３】
Ｇ成分のアルデヒド化合物としては、グルタルアルデヒド、変色性の少ない水溶性脂肪族アルデヒドが望ましい。
【００４４】
Ａ成分＋Ｂ成分＋Ｃ成分＋Ｄ成分＋Ｅ成分の合計が１００重量％から成る該防縮性成分１００重量％に対し、Ｇ成分（脂肪族アルデヒド化合物および／または芳香族アルデヒド化合物）の添加量は５．０〜１００重量％である。この添加量が５．０重量％未満と少なくては、防縮性の付加持続効果が現れない。また１００重量％よりも多くても格別、防縮性の向上が見られない。望ましいＧ成分の添加量は２０〜７０重量％である。これらのアルデヒド化合物は二種以上を併用してもよい。
【００４５】
Ａ成分＋Ｂ成分＋Ｃ成分＋Ｄ成分＋Ｅ成分の合計が１００重量％から成る該防縮性成分１００重量％に対し、 Ｆ成分２０〜２００重量％、Ｇ成分５〜１００重量％からなる獣毛製品等防縮処理剤に対して、更にＨ成分：ヒドロキシアルキルホスフィンを５０〜３００重量％添加して還元処理することにより獣毛製品等に防縮性を阻害せずに抗ピリング性を付与することができる。この添加量はＡ成分＋Ｂ成分＋Ｃ成分＋Ｄ成分＋Ｅ成分の合計が１００重量％から成る該防縮性成分１００重量％に対し、ヒドロキシアルキルホスフィンの添加量は５０〜３００重量％である。この添加量が５０重量％未満では抗ピリング効果が顕著に現れず、しかるに３００重量％を超えても格別の効果がないばかりでなく、高価となって風合いも低下する。また予め亜硫酸ナトリウム等により毛に対し還元処理を行うことにより、抗ピリング効果が一層向上する。
【００４６】
本発明に使用されるＨ成分：ヒドロキシアルキルホスフィンとしては、例えば、ジメチルヒドロキシメチルホスフィン、ジメチルヒドロキシエチルホスフィン、ジエチルヒドロキシプロピルホスフィン、トリスヒドロキシメチルホスフィン、トリスヒドロキシエチルホスフィン、トリスヒドロキシプロピルホスフィン、トリスヒドロキシブチルホスフィン、トリスヒドロキシペンチルホスフィン、トリスヒドロキシヘキシルホスフィン、トリスヒドロキシオクチルホスフィン、エチルビス（ヒドロキシエチル）ホスフィン、エチルビス（ヒドロキシプロピル）ホスフィン等を例示できる。中でもトリスヒドロキシプロピルホスフィンが好ましい。
【００４７】
またヒドロキシアルキルホスフィン誘導体としては、例えばアルキレンオキサイド付加物を使用することもできる。ヒドロキシアルキルホスフィンのアルキレンオキサイド付加物の付加モル数としては１〜７範囲のものが例示できる。上記ヒドロキシアルキルホスフィン並びにその誘導体は二種以上を併用することもできる。
【００４８】
【作用】
本発明の処理剤によって獣毛製品等の水処理、水洗濯時のクリンプ化やフェルト化を遅延させて繊維の防縮性を付与させる作用は、以下の通りと推測される。獣毛製品等の繊維は本体を構成する紡錘形の皮質細胞（コルテックス細胞：ＣＸ）の集積と、これを保護的に取り巻く扁平な鱗片状表皮細胞（クチル細胞：ＣＵ）の重積からなるケラチン化体を主成分とする。
【００４９】
皮質細胞は、架橋密度に差があるオルソコルテックとパラコルテックスの２組の張り合わせ構造をとり、バイメタル性を有し、吸湿により伸長性が異なるため、毛は弧を描いて、縮れて捲縮（クリンプ）し、湿度に応じてクリンプは伸縮現象を起こし、独特のバルキー性（嵩高性）の源となっている。
【００５０】
表皮細胞（クチクル・スケール）は、親水性を示す毛本体のコルテックス側が膨潤し易いエンドクチルからエキソクチルを経て最外層の膨潤し難く、揆水性を示すエピクチル成分がバイメタル状に張り合わせられた薄膜状の袋状の細胞からなり、酸またはアルカリ等の水溶液の作用によりスケールエッジが立ち上がり、導水性を有する細胞間充填物を通じて水の浸透を図り、繊維同士が絡まり易くなって、所謂フェルト化現象を生じ、繊維束、編織物は不可逆的に縮んでいく。
【００５１】
細胞間接合領域：コルテックス細胞とクチクル細胞の各々の間には、細胞膜錯合体（Cell Menbran Complex:ＣＭＣ）が細胞間接合物質として存在する。ＣＭ Ｃは疎水性、難水溶性、耐酵性素を有する成分が親水性を有する成分を保護し、全体が安定化している。最内層のクチクルを構成するエンドクチクルとＣＭＣは直接連結し、キャナルが形成され、コルテックス内成分と連結していることで導水管機能を発現する。水の侵入によりオルソコルテックスとパラコルテックスは伸長率の差によりクリンプを生じる。
【００５２】
アルキル基の炭素数６以上の含窒素型界面活性剤である高級脂肪酸ジアルカノールアミド等Ｆ成分とＧ成分の脂肪族アルデヒド化合物および／または芳香族アルデヒド化合物をＡ成分＋Ｂ成分＋Ｃ成分＋Ｄ成分＋Ｅ成分から構成される繊維の防縮性成分に添加して、獣毛、羊毛繊維を処理するとクチクルとクチクルの間に存在するＣＭＣのアミノ酸残基に付着し、処理剤中のアルキル基部分が疎水性を示すため、毛の内部への水の侵入を阻害してクチクルの立ち上がりを抑制し、クリンプ化とフェルト化を遅延させているものと推測される。
【００５３】
またトリスヒドロキシプロピルホスフィン、炭酸ナトリウム、亜硫酸ナトリウム、チオ硫酸ナトリウム、チオグリコール酸アンモニウム、酢酸ナトリウム、メタ硅酸ナトリウム等の水溶液をＰＨ１２以下として毛を予め還元処理しておくか、または硫酸、塩酸、モノオキシフタル酸、モノ過硫酸等の水溶液により酸化処理しておくか、または前記の多価金属塩溶液を上記の液に加えて処理すると一層、毛のクリンプ化やフェルト化が遅延できる。このことはクチクルの最外層にあるエピクチクルの疎水性を若干でも酸化還元して親水化させ、前記処理剤の組成成分の付着性を向上させて毛を柔軟にしてクチクルの立ち上がりを抑制し、毛の内部への水の侵入を阻害することによりクリンプ化とフェルト化を遅延させているものと推測される。またレーヨン等の再生繊維布にも防縮効果の発現が促進される。
【００５４】
Ｄ成分である２〜４価の金属塩もアミノ酸残基またはケラチン部分との結合を高める機能を有するためにクリンプ化とフェルト化を遅延させているものと推測される。硫酸アルミニウム６重量％水溶液に処理布を浸漬させた場合にもフェルト化の遅延効果が見られる。
【００５５】
Ａ成分＋Ｂ成分＋Ｃ成分＋Ｄ成分＋Ｅ成分からなる防縮性成分は柔軟で弾力性を有し、獣毛、羊毛等に付着させた後では、丁度糊付けしたような形態を呈し、力を加えると容易に伸長、収縮するが、力が加わらなくなると元の寸法に復元して寸法の安定化が図られる。防縮性成分は、柔軟であるため風合いの変化が少なく、むしろ向上する場合が多い。また防縮性成分は、熱可塑性を有するためスチームの噴霧やアイロン掛け等の加熱によって塑性変形させた後、常温まで冷却することにより、希望の形状、寸法にセットすることができ、さらに水に不溶性となるため、水中に浸漬処理しても繊維から脱落せず、繰り返しの水処理、水洗濯に耐えられるようになる。しかも該防縮性成分は絹、木綿、麻等の天然繊維、並びに該天然繊維を主体とした繊維製品に防縮性を与えることもできるものである。
【００５６】
また再生繊維、特にレーヨンおよびレーヨンと他の繊維との混紡による繊維質物、並びに獣毛、羊毛および獣毛、羊毛と他の天然繊維または化学繊維との混紡によって作られた撚糸では、水中に浸漬すると緩和応力が働き収縮する。このため強撚糸を用いた織物、編物は、水処理、水洗濯を行うと、収縮・変形し、取り扱いが困難であった。これらの繊維物質も本発明の処理剤の希釈水溶液中に浸漬し、応力緩和を行った後に、湿潤状態で伸長しながら乾燥させることにより収縮を大幅に低下させて製品化することができる。これは本処理剤の糊付け効果による防縮性による。
【００５７】
これらＡ〜Ｅ成分とＦ成分のアルキル基の炭素数６以上の含窒素型界面活性剤およびＧ成分の脂肪族アルデヒド化合物および／または芳香族アルデヒド化合物の各成分は次の通りに配合される。まずＡ成分である２〜６官能性ポリアルキレンオキシドポリオールとＢ成分である脂肪族ポリイソシアネートおよび／または芳香族イソシアネートおよびＥ成分である界面活性剤の所定量を配合して、温度６０〜８５℃で所定時間攪拌し、これにＤ成分である２〜４価の金属塩水溶液を加える。次にＦ成分であるアルキル基の炭素数６以上の含窒素型界面活性剤並びにＧ成分の脂肪族アルデヒド化合物および／または芳香族アルデヒド化合物を加える。次いでＣ成分である水溶性ポリウレタンおよび／または水分散性ポリウレタンエネマルジョンを加えて所定の時間攪拌することによって得られる。またＣ成分Ｆ成分は添加せずにおき、使用時に用途目的に応じたモジュラスの物を加えることもできる。またＣ成分・Ｆ成分・Ｇ成分は、上記Ａ〜Ｅ成分からなる防縮性付与成分の希釈水溶液に加えることもできる。更にＰＨ調整剤、抗菌剤、着色剤、香料、消泡剤等の補助成分を適宜の量で含有させることができる。
【００５８】
次に本発明の処理剤を用いた獣毛製品等の処理方法について説明する。羊毛等の獣毛類の毛、毛糸、織物、編物、不織布並びに毛皮の重量当たり、本処理剤の各成分をｏｗｆで必要量添加して水に希釈し、浴比３〜６０倍の処理液として使用する。この処理液中に被処理繊維を投入し、必要時間浸漬し、必要に応じ水による濯ぎ洗いを２分間×１〜２回行って脱液する。繊維が潤湿状態にある時に所定寸法に満たない場合は、所定寸法に引っ張って乾燥する。乾燥後に本処理剤の防縮成分が繊維に強固に接着し糊付けになる。乾燥後はセットされ、寸法が安定化する。繊維の適正温度でアイロン掛けを行い、シワや伸縮している部分を修正仕上げする。なお、酸処理または還元処理する場合は、防縮処理または処理液中に酸または還元剤を規定量添加して処理する。ただし、予め多価金属塩処理や酸処理または還元処理された繊維を用いる場合は、酸化剤または還元剤の添加は不要である。なお、ヒドロキシアルキルホスフィンによる還元処理を行うと、耐ピリング性が向上する。
【００５９】
処理の順序、縮絨を必要とする編物の場合、始めに編立布に対して、縮絨処理を実施する。その後、還元・酸化処理を行い毛表面にあるクチクル（スケール）部分並びにＣ、Ｍ、Ｃ部分にあるジサルファイド結合を開裂し、−Ｓ−Ｓ−結合を−ＳＨ化する。その後、水洗を行い、防縮工程に移る。
【００６０】
次いで、防縮処理を実施する。先ず、Ａ〜Ｅ成分からなる防縮性成分、Ｆ成分、Ｇ成分を溶解した溶液中に被処理物を投入し、ゆっくり攪拌して処理を行う。なお風合い調整を必要とする場合は、Ｆ成分とＧ成分の一部を前記処理後に追加して処理を行う。その後、水洗して処理を終了する。
【００６１】
本発明の処理剤の防縮性成分は、微少な含水ゲルまたはミセル状で水中に分散している。浸液中または濡れた段階では、一部の防縮成分は繊維に強固に接着するが、一部は単に繊維に付着しているにすぎない。繊維に強固に接着するのは、水分が揮散し、微少なゲルやミセルが破壊されて本発明処理剤の有効成分の一部が析出し、含水膨潤している繊維に接着されてからである。従って、脱水時に強力な遠心脱水を行ったり、絞り過ぎて含水率を２０重量％以下にすると、水と一緒に防縮成分が流出し防縮効果の発現が弱い。
【００６２】
続いて防縮処理後の繊維の水処理、洗濯方法について説明する。通常、羊毛等の獣毛類の繊維は、ドデシルベンベンスルフォン酸ナトリウム等の衣料用洗剤を加えた水溶液中で手揉み等の激しい摩擦下では１０〜６０秒間前後でクリンプ化、フェルト化現象が生じる。またポリエチレンアルキルエーテル系のノニオン系界面活性剤を主成分とするドライクリーニング表示のある繊維用毛糸洗い洗剤を使用しても家庭用洗濯機を使用する場合は、３〜５分間洗濯、２〜３分間濯ぎ洗いで水洗濯を終了するように記載されている。
【００６３】
本発明処理剤で処理した羊毛等の獣毛類の繊維製品は、前述の衣料用洗剤を加えた液中で手揉み等の激しい摩擦下でも１０分間以上の耐性を示し、さらに酸化・還元処理をした場合には、１５分間以上の耐性を示す。未処理のブランクでは１５秒前後で硬化が始まり、フェルト化が起こる。また処理布は家庭用洗濯機を用い、ドデシルベンゼンスルフォン酸ナトリウム系衣料用洗剤を加えて洗濯しても６０分間以上の耐性を示し、防縮性を有する。
【００６４】
Ｆ成分のアルキル基の炭素数６以上の含窒素型界面活性剤単独使用の効果は次の如くである。ヤシ油脂肪酸ジエタノールアミド、ラウリン酸ジエタノールアミド、エチル硫酸ラノリン脂肪酸アミノプロピルエチルジメチルアンモニウム、塩化ジステアリルジメチルアンモニウム、ポリオキシエチレンラウリルエーテル硫酸トリエタノールアミン、アルキル（１１，１３，１５）硫酸トリエタノールアミン、ヤシ油脂肪酸アミドプロピルベタイン液を用いたが防縮効果は生じなかった。しかしフェルト化の遅延効果は僅か認められ、後述の手揉み等の激しい摩擦下でも４５秒前後の耐性を示す。また本発明のＡ〜Ｅ成分及びＧ成分と併用することによって付着したＦ成分の炭素数６以上のアルキル基が疎水性を示し、毛の内部への水の侵入を阻害することにより防縮効果が認められたものと思われる。
【００６５】
Ｇ成分の脂肪族アルデヒド化合物および／または芳香族アルデヒド化合物単独使用の効果は次の如くである。
グルタルアルデヒド、変色性の少ない水溶性脂肪族アルデヒド（独、ＢＡＳＦ商品名：Relugan）を用いたが、防縮効果は認められなかった。しかし本発明の Ａ〜Ｅ成分と併用することによって効果が認められた。これは処理剤成分との架橋によりＡ〜ＦおよびＨ成分の繊維からの脱落を抑制しているものと推測される。
【００６６】
酸化剤、還元剤単独使用による効果は次の如くである。
酸化剤としてモノオキシフタル酸、モノ過硫酸塩をＰＨ３〜４、また還元剤としてメタ硅酸ナトリウム、炭酸ナトリウム、チオ硫酸ナトリウム、亜硫酸ナトリウムをＰＨ８〜１２の範囲で用いたが、単独では効果が認められなかった。還元剤抗ピリング剤としてトリスヒドロキシプロピルホスフィンを単独で用いた場合には、処理布が硬化し風合い低下を生じるが、処理直後には防縮性は認められる。しかし水洗濯を繰り返すと防縮性の低下がかなり見られた。なおピリング防止効果は、添加量が増すに従い大きくなった。しかし本発明の処理剤と併用することによって風合い改善と防縮性の持続と抗ピリング性の効果が見られた。なおトリスヒドロキシプロピルホスフィンは酵素（プロテアーゼ系）を併用すると使用量を減少しても同様の抗ピリング性を示した。ただし酵素（プロテアーゼ系）だけでは添加量も少なく、抗ピリング性の効果を示さなかった。酵素の添加量を増すと作業工程管理が難しく、且つ高価であり、獣毛繊維の強度を低下させるため、取扱には注意が必要である。これらは獣毛表面の揆水性・疎水性を弱め、繊維表面に存在し付着する量が増し、かつクチクル（スケール）の立ち上がりが少なくなったためと推察される。
【００６７】
防縮性処理と洗濯を同時に一液で実施する方法は次の通りである。後述の試験布の洗濯方法を行う際に、本発明の防縮処理剤Ａ〜Ｇ成分の規定量を洗剤と同時に注入して洗濯する。なお着用によって収縮した繊維製品は伸長して新品の長さまで復元できるようになる。
【００６８】
【実施例】
以下、実施例および比較例を示して本発明をさらに具体的に説明するが、この実施例および比較例で行う各種の試験方法は以下の通りである。
【００６９】
○繊維の収縮率：ＪＩＳ−Ｌ−１０４２法、織物の収縮率試験方法に準拠した。
【００７０】
○編み物の収縮率：▲１▼ＪＩＳ−Ｌ−１０８１・１９９０、メリヤス生地試験方法６．３０Ｇ法（家庭用電気洗濯機法）に準拠した。
▲２▼ＪＩＳ−Ｌ−１０５７、織物および編み物のアイロン収縮率試験方法、Ｂ−１法（蒸熱アイロン法）に準拠した。
本発明の防縮処理剤による処理、および水洗濯、並びに水洗濯を繰り返した場合の収縮率の計算の基となる処理前および洗濯前の測定区間の長さは、本処理剤で繊維布を処理する前の数値を用いて計算した。収縮率の計算は次式によった。
収縮率＝（処理前の測定区間の長さ−処理後の測定区間の長さ）／処理前の測定区間の長さ×１００
収縮率がマイナスの場合は伸びを示す。
【００７１】
○洗濯試験：ＪＩＳ−Ｌ−０２１７、繊維製品の取扱に関する表示記号およびその表示方法、別表記号別の試験方法、番号１０３、１０５に準拠した。
【００７２】
○ピリング試験：ＪＩＳ−Ｌ−１０７６、織物および編み物のピリング試験方法Ａ法（ＩＣＩ形試験機を用いる方法）に準拠した。
【００７３】
○風合い：未処理品を「変化なし」とした場合の各処理品の手触り等を５段階（低下、やや低下、変化なし、やや向上、向上）で比較した。
【００７４】
○手揉み洗い試験
洗剤（花王、アタック標準使用量水３０リットルに対し２０ｇの割合）を加えた水溶液中に被洗濯布を投入した後に両手の手中にて被洗濯布を丸め込んだ後に強く圧縮しながら手中で布を回して激しく、早く擦り、揉み洗いを実施した。揉み洗い後、２０秒毎に取り出し、クシャクシャになっている布を軽く引っ張り、しわ伸ばしと異形となっている部分を修正した後に縦と横の寸法を測定する。これを繰り返して１８０秒間の手揉み洗いを実施する。編み物の未処理布では１０〜６０秒で急激な収縮が通常見られる。収縮の激しい布では４０秒後には完全なフェルト化が生じる。編み物の処理布は、６０〜８０秒後では家庭用電気洗濯機でネット入り弱流洗濯を１０回程度繰り返した後の収縮率を略同程度の収縮が見られる。使用する編み物布は１０×１０（cm）のものを用いた。通常の編み物布では、水中に浸漬すると緩和応力が働き、２〜１０％の収縮が生じる。または縦・横（ウエール・コース）で収縮率が異なり変形する。編み物繊維では収縮が縦・横の各々長さ方向で６％未満では、しわ伸ばしのため引っ張ると容易に復元できる。６〜１０％の収縮では、少し力を加えた引っ張りを行うと復元できる。１０〜１９％の収縮では力を加えてひっぱりを行えば略元寸法近くに復元できるが２５％を超える収縮が生じた場合にはフェルト化が生じて復元が難しい。この手揉み洗い試験によって短時間に収縮の程度（し易さ）を判定することができる。手揉み試験の結果、収縮率の少ないものについて電気洗濯機洗いを実施して使用薬剤と添加量、並びに耐水洗濯性を定めた。なお伸びが大きい場合は、スチームを吹き付け放置冷却すれば容易に元寸法近くに復元する。
【００７５】
試験布の試験に用いた防縮処理剤のＡ〜Ｅ成分を１００重量％としたＦ成分、Ｇ成分、Ｈ成分：還元剤等の配合比率を表２に示す。
【００７６】
【表２】

【００７７】
表２の組成成分の明細は以下の通りである。

【００７８】
使用したＨ成分：還元剤、縮絨剤の明細は以下の通りである。
還元剤▲１▼：亜硫酸ナトリウム４部、チオ硫酸ナトリウム２部、炭酸ナトリウム１部の混合物
還元剤▲２▼：トリスヒドロキシプロピルホスフィン（日本化学工業、ピルゴンＰＰ−４０）抗ピリング剤
還元剤▲３▼：酵素、Ｏ，Ｗ，Ｆ、０．３％添加（日本化学工業、エンザインＷＳ；主成分プロテアーゼ系）
（注）酵素はトリスヒドロキシプロピルホスフィンの添加量を減少させても抗ピリング性の効果が認められたので用いた。
縮絨剤▲１▼：花王（株）エマール４０
縮絨剤▲２▼：三洋化成工業（株）サンデットＡＤＸ
【００７９】
試験布の防縮性処理法は以下の如くである。。
処理の順序
▲１▼縮絨処理（縮絨を必要とする編み物について実施した）
▲２▼還元処理（還元処理を必要とするものについて実施）
なお抗ピリング性を必要とするものについてトリスヒドロキシプロピルホスフィンを用いて処理した。
▲３▼防縮性処理（Ａ〜Ｇ成分を用いた）
【００８０】
［縮絨処理］
処理槽に規定量：浴比（被処理物重量当りの希釈水量の倍数、以下同じ）１：３０の５０℃温水を注入し、表２縮絨剤をＯ，Ｗ，Ｆ（被処理物重量当りの薬剤の添加量（％）以下同じ）６〜８％および合成洗剤（花王アタック）１％を添加し、均一溶液とした。この液中に被処理物を投入し、２０〜３０分間浸漬、ゆっくり攪拌した後に脱液し、水洗した。
【００８１】
［還元処理］
予め酸化・還元処理がなされていない被処理物に対して実施した。また表２、還元剤▲１▼だけで処理したものと還元剤▲１▼で処理した後に還元剤▲２▼（一部は還元剤▲３▼で示した酵素を添加）で処理したもの、還元剤▲２▼だけで処理したものの３通りの試験を実施し、主に抗ピリング性を比較した。
【００８２】
処理槽に５０℃の温水を浴比１：３０の割合で注入し、表２の還元剤▲１▼をＯ，Ｗ，Ｆで４〜６％添加し、均一液とした。この液中に被処理物を投入し、２０〜３０分間浸漬、ゆっくり攪拌した後に脱液し、水洗した。
【００８３】
［抗ピリング性付与］
トリスヒドロキシプロピルホスフィン単独処理の場合と酵素を併用した場合について試験した。結果は酵素（主成分プロテアーゼ）を併用した方がトリスヒドロキシプロピルホスフィンの添加量が少量でも同様の効果を示した。なお酵素の単独では抗ピリング性の向上が見られなかった。表３にトリスヒドロキシプロピルホスフィン並びに酵素を用いた場合の薬剤の配合割合と抗ピリング性を示す。処理布はカシミヤ編み物を用いた。
【００８４】
【表３】

【００８５】
表の説明 実施例３７〜４０、比較例１０
処理槽に５０℃温水を浴比１：３０の割合で添加、表３の薬剤を添加し、均一溶液とした。カシミヤ編み物を投入し３０分間浸漬、ゆっくり攪拌し、脱液後に水洗した。なお酵素を入れた場合は液のＰＨを３以下の有機酸を加え、酵素を失活性化させてから脱液、水洗した。その後、防縮性処理を行った後にピリング性を試験した。
【００８６】
［防縮性処理］
処理槽に４０℃温水を浴比１〜３０の割合で注入した。表２のＡ〜Ｅ成分をＯ，Ｗ，Ｆ６％、Ｆ成分のヤシ油脂肪酸ジエタノールアミド４％、Ｇ成分を２％添加し、均一溶液とする。被処理物を投入し、ゆっくり攪拌し、１０分経過後にＦ成分の第４級アンモニウム塩型カチオン界面活性剤を２％添加した。１０分経過後に脱液し、水洗した。遠心分離機で含水率３０％前後に脱水した。濡れ湿った状態の時に、予め測定しておいた被処理物の寸法と比較し、伸縮変形している場合は引っ張り修正を行い、乾燥した。または乾燥後に蒸気を吹き付け繊維を柔軟にした状態で形を修正した。
【００８７】
カシミヤ編み物製品に対し、本処理剤による処理後に水濯ぎを実施した後の収縮率を表４〜５に示す。
【００８８】
【表４】

【００８９】
表４の説明
カシミヤ編み物の試験、実施例１〜１３、比較例１はブランク（未処理とした）
１．試験布：カシミヤ１００％、平編機による編立直後の布帛を用いた。
２．収縮率▲１▼ＪＩＳ−Ｌ−１０８１Ｇ法、１０回洗濯後の値、東京都繊維工業試験所の成績書による。
▲２▼手揉み洗い試験：ウエール方向、コース方向の収縮率の平均値で算出した。
▲３▼家庭用電気洗濯機を用い、ＪＩＳ−Ｌ−０２１７．１０５法に準拠し、洗濯ネットに入れ洗濯時間を延長して洗濯を行い、３０分毎に「すすぎ」を行い、寸法を計測した。それを３回繰り返した。尚９０分洗濯後ＪＩＳ−Ｌ−１０５７．Ｂ−１法に準拠して処理し、計測してウエール方向、コース方向の収縮率の平均値で算出した。
３．ピリング試験：東京都繊維工業試験所、（財）毛製品検査協会、（財）日本化学繊維検査協会、（財）日本紡績検査協会の成績書による試験値を用いた。
４．（使用薬剤）：縮絨剤の種類、還元剤の組合せ、Ａ〜Ｈ成分の種類は表２の成分明細に示した薬剤を用いた。
【００９０】
【表５】

【００９１】
表５の説明 カシミヤニット洗濯収縮率 実施例１４
試験布：実施例５の試験布を用いた。使用薬剤：実施例５と同一にした。
試験方法：ＪＩＳ−Ｌ−１０１８−１９９０ メリヤス生地試験方法６．３０Ｇ法（家庭用電気洗濯機法）
ただしＪＩＳ−Ｌ−０２１７（繊維製品の取り扱いに関する表示記号およびその寸法表示方法）の別表、記号別の試験方法の（１）洗い方番号１０５に規定する試験方法による。
乾燥：スクリーン乾燥。洗剤：中性のアクロンを使用した。試験は同一材料について「洗濯、乾燥、測定」を１０回繰り返し、１回毎に当初の長さを基準に収縮率を算出した。
（注）東京都繊維工業試験所の成績書による試験値を用いた。
【００９２】
【表６】

【００９３】
表６の説明 実施例１５〜１９、比較例２はブランク（未処理）とした。
１．試験布：羊毛１００％、梳毛糸ニット、平編布
２．収縮率▲１▼手揉み洗い試験：ウエール方向、コース方向の収縮率の平均値で算出した。
▲２▼家庭用電気洗濯機を用い、ＪＩＳ−Ｌ−０２１７，１０５方に準拠し、洗濯ネットとに入れ洗濯時間を延長して洗濯を行い、３０分毎に「すすぎ」を行い、寸法を計測した。それを３回繰り返した。なお９０分洗濯後にＪＩＳ−Ｌ−１０５７，Ｂ−１方に準拠して処理し、計測してウエール方向、コース方向の収縮率の平均値で算出した。
３．（使用薬剤）：Ａ〜Ｈ成分の組合せは、表２の成分明細に示した薬剤を用いた。
【００９４】
【表７】

【００９５】
表７の説明 実施例２０〜２６、比較例３はブランク（未処理）とした。
１．試験布：羊毛とアンゴラ混紡による紡毛糸を使用した綾編みによる厚手の編み物布
２．収縮率：▲１▼手揉み洗い試験
▲２▼家庭用電気洗濯機試験
表６の収縮率の試験方法、計算方法と同様とした。
３．（使用薬剤）：Ａ〜Ｈ成分の組合せは表２の成分明細に示した薬剤を用いた。
【００９６】
【表８】

【００９７】
（表８の説明）
１．試験に使用したニット（編み物）製品
ニット（編み物）製品の洗濯後の収縮率
ニット▲１▼：カシミヤ１００％平編セーター 重量２５０ｇ
ニット▲２▼：羊毛１００％梳毛糸セーター 重量４８０ｇ
ニット▲３▼：羊毛１００％紡毛糸使用セーター 重量２８０ｇ
ニット▲４▼：羊毛８０％モヘヤ２０％紡毛糸セーター 重量６７５ｇ
【００９８】
２．試験製品に使用した薬剤並びに処理法法
実施例２７〜３０の処理には、実施例１３の使用薬剤と処理方法と同一にした。
【００９９】
３．洗濯方法
（１）ＪＩＳ−Ｌ−０２１７−１０５法（電機洗濯機洗い、洗濯ネット使用）に準拠した。
（２）第２回目の洗濯は、初回洗濯後の製品セーターを用い、ＪＩＳ−Ｌ−０２１７−１０５法（洗濯ネット使用）に準拠し、洗濯時間だけを延長し３０分間の連続した洗濯を実施した。
（３）第３回目の洗濯は、第２回目洗濯後の製品セーターを用いて第２回目と同様に３０分間の連続した洗濯を実施した。
（４）製品セーターは、洗濯濯ぎ、脱水後は縮れ、シワが多いため、脱水後の湿潤状態の時にパンパンと引っ張りを行って、シワ伸ばしを実施してから二つ折りとし、吊り干し乾燥を行った。
【０１００】
４．収縮性
（１）洗濯乾燥後の製品セーターについて、身の丈、身巾（上部、腋下）、身巾（下部・裾）、袖丈、袖先巾の寸法を計測して記入した。
（２）洗濯前の寸法は、防縮処理、乾燥後の寸法を計測して記入した。
（３）処理前の寸法は、防縮処理をする前の製品セーターの寸法を計測して記入した。
（４）仕上げ後の寸法は、３回目（６０分）洗濯、乾燥後に寸法を計測したセーターに対して、蒸気と熱風を吹き付けて寸法修正を行った後、冷却してから寸法を計測して記入した。
（注）６０分間洗濯後のセーターは、フェルト化が進行していないため、引っ張りを行うと容易に伸長する。また蒸気を吹き付けると更に容易に寸法修正が可能であった。
【０１０１】
【表９】

表９の説明 織物の洗濯後の収縮率
１．使用した織物布
織物布でありながら編み物のように引っ張ると容易に伸縮し、かつ水中に浸漬すると収縮、変形する寸法が不安定な縫製時の取り扱いが難しい布を中心に試験した。
（１）常態寸法：容易に伸縮する目安として常態（室温放置時、以下同じ）で計測した値を「常態寸法」とした。
（２）常態引っ張り寸法：常態で引っ張って伸ばしたままの状態で計測し「常態引っ張り寸法」とした。
（３）洗濯前（処理後）寸法：試験布は、緩和応力が働き収縮した。
比較例では：３５℃温水のみに１５分間浸漬してから乾燥後に寸法を計測し記入した。
実施例では：水に浸漬しない未処理布を用いて防縮処理を行い、乾燥後に寸法を計測し記入した。
【０１０２】
（４）試験布の種類
布−１：羊毛１００％強撚糸（１６００回／ｍ）伸縮性薄地粗織布（株）花井利製
布−２：羊毛１００％強撚糸（１６００回／ｍ）伸縮性薄地密織布（株）花井利製
布−３：羊毛強撚糸、伸縮性厚地粗織布 （株）花井利製
布−４：羊毛９０％ナイロン１０％羅紗織厚地織布 （株）花井利製
布−５：羊毛１００％縞綾織布 （株）花井利製
【０１０３】
２．試験布の処理に使用した薬剤並びに処理方法
比較例４〜７はブランクとし、前述温水だけに浸漬した布を用い、薬剤処理を実施しなかった。
実施例３１〜３５は、実施例１３の使用薬剤と処理方法と同一にした。
【０１０４】
３．洗濯方法（１）ＪＩＳ−Ｌ−０２１７−１０５法（電機洗濯機洗い）に準拠した。
（２）第２回目の洗濯は、初回洗濯後の布を用い、ＪＩＳ−Ｌ−０２１７−１０５法に準拠し、洗濯時間だけを延長し、３０分間の連続した洗濯を実施した。
（３）第３回目の洗濯は、第２回目洗濯後の布を用いて、第２回目と同様に３０分間の連続した洗濯を実施した。
【０１０５】
４．収縮率
（１）洗濯・すすぎ乾燥後の布を用い、縦方向と横方向の寸法を計測し、常態寸法との差から算出した。
（２）今回、試験した布では、伸縮性を有するためか、前の回より次の回の方が収縮率が少ない布があったが、比較例と実施例の測定値から防縮効果の傾向は得られた。
【０１０６】
【表１０】

【０１０７】
（表１０の説明）毛皮（ムートン）洗濯後の収縮率
１．試験毛皮：羊毛の長さ２３mmのムートン（クロム鞣し）
２０cm×２０cm（７０ｇ）×２枚
【０１０８】
２．処理剤の種類
イ．表２ 組成３のＡ〜Ｅからなる防縮成分（１００％）を用いた。
ロ．表２ Ｆ成分１２５％を用いた。
ハ．表２ Ｇ成分３３％を用いた。
ニ．表２ Ｈ成分還元剤、抗ピリング剤１３３％を用いた。
（注）比較例−９はブランクとし、何の処理も実施しなかった。
【０１０９】
３．薬剤処理の順序と寸法
（１）Ａ〜Ｅ成分：Ｏ，Ｗ，Ｆ３％、浴比１：３０、３０℃浴中にムートンを浸漬し、１０分間攪拌し、５０分間静止して計５時間浸漬した。
（２）Ｈ成分還元剤２、抗ピリング剤：Ｏ，Ｗ，Ｆ１０％、第２燐酸ナトリウム７水和塩２ｇ／リットル、ノニオン界面活性剤１％、浴比１：３０、３０分間液中にムートンを浸漬後、脱液し水洗した。
（３）Ｏ，Ｗ，Ｆ：Ｇ成分２％、Ｆ成分６％、Ａ〜Ｅ成分３％、浴比１：３０、３０℃液中に３０分間浸漬後、脱液し、水洗した。
【０１１０】
４．洗濯方法（電機洗濯機洗い）
（１）ＪＩＳ−Ｌ−０２１７−１０５法に準拠した（洗濯ネット使用）
（２）第２回目は初回洗濯後の毛皮（ムートン）を用い、ＪＩＳ−Ｌ−０２１７−１０５法に準拠し、洗濯時間だけを延長し、３０分間の連続した洗濯を実施した。
（３）第３回目の洗濯は、第２回目洗濯後の毛皮（ムートン）を用いて、第２回目と同様に３０分間の連続した洗濯を実施した。
【０１１１】
５．収縮率
（１）洗濯・すすぎ、乾燥後の毛皮（ムートン）を用い、縦方向、横方向の寸法を計測し、処理前の寸法との差から算出した。
（２）変化率：防縮剤で処理したことによる寸法の変化を示す。
（３）収縮率、変化率の基となる寸法は、処理前の寸法を用いた。
【０１１２】
【発明の効果】
以上説明したように、本発明によれば、獣毛製品等に対して水処理時間を延長したり、或いは水洗濯の回数を増やしたりしても、防縮効果を持続させることができ、また抗ピリング性を有する。従って、本発明で処理した獣毛製品等は、水処理・水洗濯を繰り返してもクリンプ化やフェルト化が遅延されるため、寸法安定性や柔軟性、風合い等が向上するという特長を有し、しかも編み目の粗い編み物や水に浸漬するだけで収縮しやすい強撚糸の織物布等の製品に対しても収縮率を減少させることができるものである。さらに本発明で処理した獣毛製品等は、水道水に洗剤を加えて繰り返し洗濯を行い、これを直射日光に曝して乾燥させても毛羽立ちが少なく、外観変化も少なく、柔軟性、寸法安定性が失われないばかりか、耐ピリング性、機械的強さ 、耐屈曲性、耐摩耗性、適度な保温性、保湿性、通気性、吸放湿性、等の特性も変化しないという優れた効果を奏することができる。[0001]
BACKGROUND OF THE INVENTION
In the present invention, when a fiber product or fur made from wool, animal hair or the like (hereinafter referred to as animal hair product) is subjected to water treatment such as washing and dyeing, the animal hair product is deformed or hardened. And a treatment method using the treatment agent.
[0002]
[Prior art]
Conventionally, when water treatment such as water washing of animal hair products etc. is performed, dry cleaning is performed because deformation (shrinkage and elongation), appearance change (felting, crimping, fluffing), flexibility change (curing, texture) occur Has been made. Alternatively, an animal hair product or the like has been washed in lukewarm water using a detergent mainly composed of a nonionic surfactant such as polyoxyethylene alkyl ether. However, the cleaning using the detergent has a problem that shrinkage and hardening occur even if the washing is performed in warm water. In particular, when animal hair products or the like are immersed in a detergent solution for a long time, the shrinkage becomes severe.
[0003]
Therefore, measures have been taken to prevent shrinkage from the raw material for water treatment such as washing and dyeing of animal hair products and the like. Examples of means for preventing shrinkage of animal hair products include an oxidation method, a softening method, and a resin method.
[0004]
In the oxidation method, a cuticle (scale) present on the surface of a fiber such as animal hair products is treated with an enzyme or chlorine.
[0005]
The softening method is to soften animal hair products and the like when wet to prevent entanglement between fibers, and includes a Dylan FTC method, a protein method, and the like.
[0006]
The resin method is to prevent movement of fibers during washing by bonding fibers such as animal hair products with resin, or to prevent entanglement between fibers by covering the scale with resin, Examples include IWS chlorination / resin method, Croy resin method, Shirolane BAP method, DC-109 method and the like.
[0007]
[Problems to be solved by the invention]
By the way, in the oxidation method, since the cuticle (scale) is removed, there is a problem that the texture is changed and the fibers are easily frayed. Further, the flexible method has a drawback that fibers of animal hair products and the like become slippery and the fibers are easily frayed. Furthermore, in the resin method, animal hair products and the like are cured and the texture is lowered, and once contracted and felted, the original dimensions cannot be restored.
[0008]
The present inventor previously provided a treating agent for a fibrous material in Japanese Patent No. 2525507, Japanese Patent No. 2561752, Japanese Patent No. 2639790, Japanese Patent No. 2568329, and Japanese Patent Laid-Open No. 7-11584. However, these treatment agents have been rapidly crimped and felted under harsh conditions such as stirring in water for a long period of time and washing with stagnation. In Japanese Patent Application No. 9-341935, the ability to maintain the shrinkage resistance of animal hair products and the like was weak. An object of the present invention is to provide a treatment agent and a treatment method for preventing shrinkage and hardening of animal hair products and the like in conventional water treatment.
[0009]
[Means for Solving the Problems]
The present inventor has found that the crimping and felting are delayed by delaying the penetration of water into the interior of the animal hair fiber and the rise of the cuticle (scale), thereby completing the present invention.
[0010]
  In the first invention of the present invention, as the shrink-proof component,
  A component: 2 to 6 functional polyalkylene oxide polyol is 5 to 80% by weight,
  Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6 functional polyalkylene oxide polyol,
  Component C: 5-94.7% by weight of water-soluble polyurethane and / or water-dispersible polyurethane,
  Component D: 0.1 to 7% by weight of 2 to 4 metal salt,
  E component: Surfactant (excluding nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group) is 0.1 to 20% by weight,
Essentially consists of (However,A component + B component + C component + D component + E component is 100% by weight in total)
  For 100% by weight of the shrink-proof component,
  F component: 20 to 200% by weight of a nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms,
  G component: Aliphatic aldehyde compound and / or aromatic aldehyde compound 5 to 100% by weight
Solid or liquid containingFor animal hair productsIt is an anti-shrink treatment agent.
[0011]
  Further, the second invention of the present invention is a shrink-proof component,
  A component: 2 to 6 functional polyalkylene oxide polyol is 5 to 80% by weight,
  Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6 functional polyalkylene oxide polyol,
  Component C: 5-94.7% by weight of water-soluble polyurethane and / or water-dispersible polyurethane,
  Component D: 0.1 to 7% by weight of 2 to 4 metal salt,
  E component: Surfactant (however, excluding nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group) is 0.1 to 20% by weight,
Essentially consists of (However,A component + B component + C component + D component + E component is 100% by weight in total)
For 100% by weight of the shrink-proof component,
  F component: 20 to 200% by weight of a nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms,
  G component: Aliphatic aldehyde compound and / or aromatic compound 5 to 100% by weight
Solid or liquid containingFor animal hair productsIn the anti-shrink agent,Delaying the felting of animal hair products, etc. by immersing animal hair products, etc. for a certain period of time
A method for preventing shrinkage of animal hair products characterized by
[0012]
  The third invention of the present invention is a shrink-proof component.,
  A component: 2 to 6 functional polyalkylene oxide polyol is 5 to 80% by weight,
  Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6 functional polyalkylene oxide polyol,
  Component C: 5-94.7% by weight of water-soluble polyurethane and / or water-dispersible polyurethane,
  Component D: 0.1 to 7% by weight of 2 to 4 metal salt,
  E component: Surfactant (However,0.1 to 20% by weight) (excluding nitrogen-containing surfactants having an alkyl group with 6 or more carbon atoms)
Essentially consists of (However,(A component + B component + C component + D component + E component total is 100 wt%),
  For 100% by weight of the shrink-proof component,
  F component: 20 to 200% by weight of a nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms,
  G component: Aliphatic aldehyde compound and / or aromatic aldehyde compound 5 to 100% by weight,
  H component: hydroxyalkylphosphine 50 to 300% by weight
Solid or liquid containing
For animal hair productsIt is an anti-shrink treatment agent.
[0013]
  The fourth invention of the present invention is a shrink-proof component.,
  A component: 2 to 6 functional polyalkylene oxide polyol is 5 to 80% by weight,
  Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6 functional polyalkylene oxide polyol,
  Component C: 5-94.7% by weight of water-soluble polyurethane and / or water-dispersible polyurethane, Component D: 0.1-7% by weight of divalent to tetravalent metal salt,
  E component: Surfactant (However,0.1 to 20% by weight) (excluding nitrogen-containing surfactants having an alkyl group with 6 or more carbon atoms)
Essentially consists of (However,(A component + B component + C component + D component + E component total is 100 wt%),
  For 100% by weight of the shrink-proof component,
  F component: 20 to 200% by weight of a nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms,
  G component: Aliphatic aldehyde compound and / or aromatic aldehyde compound 5 to 100% by weight,
  H component: hydroxyalkylphosphine 50 to 300% by weight
Solid or liquid containingFor animal hair productsIn the anti-shrink agent,Animal hair productsEtc. for a certain period of timeAnimal hair productsReduce the occurrence of pilling and delay felting
Characterized byAnimal hair productsThis is the shrinking treatment method.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The amount of component A added is 5 to 80% by weight, preferably 8 to 70% by weight. If the component A is less than 5% by weight, the effect of preventing shrinkage of animal hair products after washing with water will not appear, and even if more than 80% by weight is added, no further effect can be expected.
[0015]
The addition amount of B component is 0.1-20 weight%, Preferably it is 0.2-15 weight%. If the B component is less than 0.1% by weight, the effect of preventing shrinkage of animal hair products after washing with water will not appear, and if it exceeds 20% by weight, the liquid will thicken and become difficult to use.
[0016]
The amount of component C added is 5-94.7% by weight, preferably 10-70% by weight. If the C component is less than 5% by weight, the shrinkage-preventing effect of animal hair products after washing with water does not appear, and if it exceeds 94.7% by weight, no particular effect appears.
[0017]
The addition amount of D component is 0.1 to 7 weight%, Preferably it is 0.2 to 5 weight%. If the D component is less than 0.1% by weight, the effect of preventing shrinkage of the animal hair product after washing does not appear. However, if it exceeds 7% by weight, the stability of the liquid also deteriorates and the texture is lowered. .
[0018]
The added amount of the E component is 0.1 to 20% by weight. When the E component is less than 0.1% by weight, the stability of the liquid is poor and the permeation effect on the fiber does not appear. However, the effect of adding only 20% by weight cannot be expected.
[0019]
In the present invention, the F component is contained in an amount of 20 to 200% by weight, preferably 30 to 200% by weight, and the F component is 20% by weight with respect to 100% by weight of the above A, B, C, D and E components. If the ratio is less than 200% by weight, the effect of preventing shrinkage that delays hardening and shrinkage associated with felting of animal hair products and the like does not appear.
[0020]
The shrink-proof component contains a polyalkylene oxide polyol having 2 to 6 functional groups, preferably 2 to 4 functional groups, and most preferably trifunctional as the A component. The molecular weight of such a polyalkylene oxide polyol is preferably 600 to 10,000, more preferably 2,000 to 6,000. The alkylene oxide that is a raw material of the polyalkylene oxide polyol may be ethylene oxide, propylene oxide, 1,2- or 2-3 butylene oxide, or a combination of two or more thereof.
[0021]
Polyols that are raw materials for polyalkylene polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, 1,4-butanediol, 1,6-hexanediol, glycerin triol, C₈~ C_{twenty four}Aliphatic triol, C₉~ C_{twenty four}An aliphatic unsaturated polyhydric alcohol etc. can be illustrated.
[0022]
The B component can contain aliphatic or aromatic isocyanates that are end-treated with 2-6 functional, preferably 2-4 functional, most preferably trifunctional polyalkylene oxide polyols. The component B can be obtained by reacting an aliphatic isocyanate or aromatic isocyanate with a large excess of a 2-6 functional polyalkylene oxide polyol and protecting the isocyanate group at the terminal with a polyol.
[0023]
Examples of the aliphatic isocyanate and / or aromatic isocyanate include hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, mono- or poly-hexamethylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, phenylene diisocyanate, polyisocyanate. Examples include methylene polyphenyl polyisocyanate and xylene diisocyanate. Of these, polyhexamethylene diisocyanate and isophorone diisocyanate are preferred. On the other hand, as a 2-6 functional polyalkylene oxide polyol, the above-mentioned polyol is used as A component.
[0024]
As the water-soluble polyurethane and / or water-dispersible polyurethane of component C, (1) water-soluble polyurethane (non-reactive type), (2) water-dispersed polyurethane (non-reactive type, forced emulsification type), and (3) water-dispersed Type polyurethane (non-reactive type, self-emulsifying type), and (4) reactive water-soluble or water-dispersible polyurethane (forced emulsifying type, self-emulsifying type).
[0025]
Among these polyurethanes (1) to (4), the water-soluble polyurethane (1) (1) and the water-dispersed polyurethane (3) (non-reactive, self-emulsifying) (3) are preferred in the present invention. Table 1 shows the resin physical properties of polyurethanes (1) to (4) above.
[0026]
The polyurethane of (1) to (4) above may be any polyurethane as long as its physical properties are in the range shown in Table 1, depending on the use of the object, and can be applied according to the purpose of use. .
[0027]
[Table 1]

[0028]
In Table 1, the hardness was measured using a D durometer specified in JIS-K-7215. The 100% modulus and elongation rate were measured at a temperature of 23 ° C. by producing a 0.3 mm film. The measuring method was based on JIS-K-6301.
[0029]
The preferred amount of the water-soluble polyurethane or water-dispersible polyurethane is 5-94.7% by weight, more preferably 10-70% by weight, and further preferably 15-60% by weight. When the blending amount is increased, shrinkage is prevented even if the fiber treated with the treatment agent of the present invention is repeatedly subjected to water treatment or water washing. If the amount exceeds 94.7% by weight, the texture of animal hair products and the like changes, which is not preferable. If the amount is less than 5% by weight, the dimensional stability does not appear. Two or more of these water-soluble polyurethanes or water-dispersible polyurethanes can be used in combination.
[0030]
The divalent to tetravalent metal salt of component D is a metal salt of an inorganic acid or an organic acid, preferably a trivalent to tetravalent metal salt, more preferably a trivalent metal salt. Specifically, divalent metal salts such as copper salt, zinc salt, calcium salt and magnesium salt, trivalent metal salts such as aluminum salt, chromium salt, iron salt, lanthanum salt and cerium salt, and zirconium salt And tetravalent metal salts such as silicon salts. Examples of the aluminum salt include sodium aluminate, aluminum sulfate, aluminum ammonium sulfate, aluminum nitrate, aluminum acetate, aluminum fluoride, aluminum chloride, aluminum oxalate, and aluminum lactate. Examples of the zirconium salt include zirconium sulfate. Of these, aluminum sulfate is preferred, and a combination with other metal salts is also preferred.
[0031]
Non-ionic surfactants for component E (except for nitrogen-containing surfactants with an alkyl group having 6 or more carbon atoms)systemA surfactant is preferable, and a combination of a nonionic surfactant and an anionic surfactant or a combination of a nonionic surfactant and a cationic surfactant is preferable, and an amphoteric surfactant is also used.
[0032]
As the nonionic surfactant, an ethylene oxide adduct of alkylphenol is preferable. Polyoxyethylene polyoxypropylene alkyl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether having 1 to 20 moles of ethylene oxide having an average carbon number of 6 to 12 alkyl groups, fatty acids having an alkyl group of less than 6 carbon atoms (Mono) dialkylamide or alkylamine, plant fatty acid ester, alkyl saccharoid, fatty acid glycerin monoester, polyoxyethylene having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 mol ethylene oxide added thereto Examples thereof include alkyl or alkenyl ether.
[0033]
Moreover, the following can be mentioned as an anionic surfactant.
(1) Alkali metal salt of higher fatty acid (soap)
(2) Alkyl group or alkenyl sulfate having a linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 20 and having an average of 0.5 to 8 moles of ethylene oxide added in one molecule
(3) Alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16
(4) Alkyl or alkenyl sulfate having an alkyl group or alkenyl group having an average carbon number of 10 to 20
(5) Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule (6) Alkane sulfonate having an average of 10 to 20 carbon atoms in one molecule
(7) Sulfosuccinate sodium salt
(8) Ether carboxylate
(9) Higher alcohol ethoxylate
(10) Higher alcohol sulfate
(11) Monoalkyl phosphate
(12) Alkyl polyglycoside
Etc. can be illustrated.
[0034]
As a cationic surfactant
(1) Aliphatic primary, secondary, tertiary amine salts and aliphatic quaternary ammonium
(2) Aromatic quaternary ammonium salt
(3) Heterocyclic quaternary ammonium salt
(4) Benzethonium chloride
(5) Pyridinium salt
(6) Imidazolinium salt
Etc. can be illustrated.
[0035]
As amphoteric surfactants,
(1) Alkyl betaine type
(2) Amidobetaine type
Etc.
[0036]
Each of the nonionic surfactant, the anionic surfactant, the cationic surfactant and the amphoteric surfactant may be used in combination of two or more.
[0037]
Examples of the nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group of component F include coconut oil fatty acid diethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide, lauric acid diethanolamide, coconut oil fatty acid monoethanolamide, stearyl acid Examples thereof include mono (di) ethanolamide, lauric acid isopropanolamide, polyoxyethylene alkylamine, and alkylamino oxide. Of these, nonionic surfactants such as water-soluble lauric acid diether amide and coconut oil fatty acid diethanolamide are preferable.
[0038]
Examples of the nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group of component F include lanolin ethyl sulfate fatty acid aminoproleethyldimethylammonium chloride, distearylmethylammonium chloride, stearyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, stearyl chloride Quaternary ammonium salt type cationic surfactants such as trimethylammonium, cetyltrimethylammonium chloride, benzalkonium chloride (R is mainly lauryl group) and the like can be exemplified.
[0039]
Examples of the nitrogen-containing surfactant having 6 or more carbon atoms of the alkyl group of the F component include coconut oil fatty acid amidopropyl betaine, lauric acid amidopropyl betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxyl-N-. Examples thereof include amphoteric surfactants such as hydroxyethylimidazolinium betaine, sodium N-lauroyl-N′hydroxyethylethylenediamine, sodium β-laurylaminopropionate, and the like.
[0040]
Examples of the F component include the polyamide-based cationic surfactants, nonionic / cationic surfactants, nonionic surfactants, quaternary ammonium salt type cationic surfactants, and amphoteric surfactants. By changing the type of these surfactants, it is possible to change the shrinkage resistance and texture (flexibility, fluffiness, sliminess, hand feeling, etc.) after the treatment. Among these, nitrogen-containing surfactants having natural fatty acids such as coconut oil fatty acid and lanolin fatty acid in the alkyl group are desirable. Two or more of these surfactants may be used in combination.
[0041]
Examples of the aliphatic aldehyde compound of component G include acetaldehyde, paraacetaldehyde, metaacetaldehyde, butyraldehyde, hydroxybutyraldehyde, glutaraldehyde, crotonaldehyde, margaraldehyde, and the like.
[0042]
Examples of the G component aromatic aldehyde compound include benzaldehyde, hydroxybenzaldehyde, formaldehyde, cinnamaldehyde, and the like.
[0043]
As the aldehyde compound of component G, glutaraldehyde and a water-soluble aliphatic aldehyde with little discoloration are desirable.
[0044]
The addition amount of G component (aliphatic aldehyde compound and / or aromatic aldehyde compound) is 5.0% with respect to 100% by weight of the non-shrinkable component in which the total of A component + B component + C component + D component + E component is 100% by weight. ~ 100% by weight. If the amount added is less than 5.0% by weight, the anti-shrinking effect of addition persistence does not appear. Further, even if the amount is more than 100% by weight, no particular improvement in shrinkage resistance is observed. A desirable addition amount of the G component is 20 to 70% by weight. Two or more of these aldehyde compounds may be used in combination.
[0045]
Anti-shrinkage of animal hair products consisting of 20 to 200% by weight of F component and 5 to 100% by weight of G component against 100% by weight of the non-shrinking component consisting of 100% by weight of A component + B component + C component + D component + E component By adding 50 to 300% by weight of the H component: hydroxyalkylphosphine to the treatment agent, reduction treatment can be imparted to animal hair products and the like without inhibiting shrinkage resistance. The amount of addition of hydroxyalkylphosphine is 50 to 300% by weight with respect to 100% by weight of the non-shrinkable component in which the total of component A + B component + C component + D component + E component is 100% by weight. When this addition amount is less than 50% by weight, the anti-pilling effect does not appear remarkably. However, when it exceeds 300% by weight, not only is there no particular effect, but the cost is increased and the texture is lowered. Moreover, the anti-pilling effect is further improved by reducing the hair with sodium sulfite or the like in advance.
[0046]
H component used in the present invention: Examples of the hydroxyalkyl phosphine include dimethylhydroxymethylphosphine, dimethylhydroxyethylphosphine, diethylhydroxypropylphosphine, trishydroxymethylphosphine, trishydroxyethylphosphine, trishydroxypropylphosphine, trishydroxybutyl. Examples include phosphine, trishydroxypentylphosphine, trishydroxyhexylphosphine, trishydroxyoctylphosphine, ethylbis (hydroxyethyl) phosphine, ethylbis (hydroxypropyl) phosphine, and the like. Of these, trishydroxypropylphosphine is preferable.
[0047]
As the hydroxyalkylphosphine derivative, for example, an alkylene oxide adduct can be used. Examples of the number of moles added of the alkylene oxide adduct of hydroxyalkylphosphine can range from 1 to 7. Two or more of the above hydroxyalkyl phosphines and derivatives thereof can be used in combination.
[0048]
[Action]
The effect | action which delays the water treatment of animal hair products etc. with the treatment agent of this invention, and crimping and felting at the time of water washing, and provides the shrinkage resistance of a fiber is estimated as follows. The fiber of animal hair products and the like is a keratin consisting of accumulation of spindle-shaped cortical cells (cortex cells: CX) constituting the main body and a pile of flat scaly epidermal cells (cutyl cells: CU) surrounding this in a protective manner. The main component is a chemical compound.
[0049]
Cortical cells have two laminated orthocortic and paracortex structures with different crosslink density, bimetallic properties, and different extensibility due to moisture absorption. (Crimping), and crimping causes expansion and contraction depending on the humidity, and is a source of unique bulkiness (bulkyness).
[0050]
The epidermis cells (cuticle scale) are a thin film in which the cortex side of the hair body showing hydrophilicity is easy to swell from the endoctyl to the outermost layer via octoctyl, and the epioctyl component showing hydrophobicity is laminated in a bimetallic form. Made of pouch-like cells, the scale edge rises due to the action of an aqueous solution such as acid or alkali, penetrates water through the intercellular packing having water conductivity, and the fibers tend to get entangled, resulting in a so-called felting phenomenon. Fiber bundles and knitted fabrics shrink irreversibly.
[0051]
Intercellular junction region: Between each of the cortex cells and the cuticle cells, a cell membrane complex (Cell Menbran Complex: CMC) exists as an intercellular junction substance. In CMC, components having hydrophobicity, poorly water-soluble property, and fermentation-resistant element protect components having hydrophilicity, and the whole is stabilized. Endocicles and CMCs constituting the innermost cuticle are directly connected to form a canal, and a conduit function is manifested by being connected to cortex components. The intrusion of water causes crimping between orthocortex and paracortex due to the difference in elongation.
[0052]
A higher fatty acid dialkanolamide, such as a nitrogen-containing surfactant having an alkyl group of 6 or more carbon atoms, and an aliphatic aldehyde compound and / or an aromatic aldehyde compound of the G component are mixed into the A component + B component + C component + D component + E component When animal hair and wool fiber are treated with the anti-shrinking component of the fiber composed of the above, it adheres to the amino acid residues of CMC existing between the cuticle and the cuticle, and the alkyl group portion in the treatment agent becomes hydrophobic. For this reason, it is presumed that the penetration of water into the hair is inhibited to suppress the rise of the cuticle, and the crimping and felting are delayed.
[0053]
In addition, the hair is reduced in advance with an aqueous solution of trishydroxypropylphosphine, sodium carbonate, sodium sulfite, sodium thiosulfate, ammonium thioglycolate, sodium acetate, sodium metasuccinate and the like having a pH of 12 or less, or sulfuric acid, hydrochloric acid, Oxidation treatment with an aqueous solution of monooxyphthalic acid, monopersulfuric acid or the like, or addition of the above polyvalent metal salt solution to the above-mentioned solution can further delay hair crimping or felting. This means that the epicuticle in the outermost layer of the cuticle is slightly reduced in hydrophobicity by hydrophilization, improves the adhesion of the composition of the treatment agent, softens the hair, suppresses the rise of the cuticle, It is presumed that crimping and felting are delayed by inhibiting the intrusion of water into the inside. In addition, the expression of the shrink-proof effect is also promoted in the recycled fiber cloth such as rayon.
[0054]
It is presumed that crimping and felting are delayed because the divalent to tetravalent metal salt which is the D component also has a function of enhancing the binding with the amino acid residue or keratin moiety. Even when the treated cloth is immersed in a 6% by weight aqueous solution of aluminum sulfate, a felting delay effect is observed.
[0055]
The shrink-proof component consisting of A component + B component + C component + D component + E component is flexible and elastic, and after adhering to animal hair, wool, etc., it is just glued and easy to apply force However, when the force is no longer applied, the original dimensions are restored and the dimensions are stabilized. The shrink-proof component is flexible and therefore has little change in texture, but rather improves in many cases. In addition, since the shrink-proof component has thermoplasticity, it can be set to the desired shape and dimensions by cooling to room temperature after plastic deformation by heating such as steam spraying or ironing, and is insoluble in water. Therefore, even if it is immersed in water, it does not fall off from the fibers, and can withstand repeated water treatment and water washing. In addition, the shrink-proof component can impart shrink-proof properties to natural fibers such as silk, cotton, hemp and the like, as well as to fiber products mainly composed of the natural fibers.
[0056]
Also, regenerated fibers, especially fiber products made from rayon and blends of rayon and other fibers, and twisted yarns made by blending animal hair, wool and animal hair, wool and other natural fibers or chemical fibers, are immersed in water. Then, relaxation stress works and shrinks. For this reason, woven fabrics and knitted fabrics using strong twisted yarns are shrunk and deformed when treated with water and washed with water, and are difficult to handle. These fiber materials are also immersed in a dilute aqueous solution of the treatment agent of the present invention, subjected to stress relaxation, and then dried while being stretched in a wet state, thereby making it possible to produce a product with greatly reduced shrinkage. This is due to the shrinkage resistance due to the gluing effect of this treatment agent.
[0057]
The nitrogen-containing surfactant having 6 or more carbon atoms of the alkyl groups of the components A to E and the component F and the components of the aliphatic aldehyde compound and / or the aromatic aldehyde compound of the component G are blended as follows. First, a predetermined amount of a 2- to 6-functional polyalkylene oxide polyol as component A, an aliphatic polyisocyanate as component B and / or an aromatic isocyanate and a surfactant as component E is blended, and a temperature of 60 to 85 ° C. And a 2 to 4 valent metal salt aqueous solution, which is a component D, is added thereto. Next, a nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group as the F component and an aliphatic aldehyde compound and / or an aromatic aldehyde compound as the G component are added. Next, it is obtained by adding water-soluble polyurethane and / or water-dispersible polyurethane energy as component C and stirring for a predetermined time. Further, the C component and the F component are not added, and a modulus product corresponding to the purpose of use can be added at the time of use. Further, the C component, the F component, and the G component can be added to a dilute aqueous solution of the anti-shrinkage imparting component composed of the components A to E. Furthermore, auxiliary components such as a pH adjuster, an antibacterial agent, a colorant, a fragrance, and an antifoaming agent can be contained in an appropriate amount.
[0058]
Next, the processing method of animal hair products etc. using the processing agent of this invention is demonstrated. A treatment solution having a bath ratio of 3 to 60 times by adding a necessary amount of each component of this treatment agent by owf to the weight of animal hair such as wool, yarn, woven fabric, knitted fabric, non-woven fabric and fur, and diluting in water. Use as The fibers to be treated are put into this treatment liquid, immersed for a necessary time, and rinsed with water as necessary for 2 minutes × 1 to 2 times to remove the liquid. If the fiber is less than the predetermined size when it is in a moist state, it is pulled to the predetermined size and dried. After drying, the shrink-resistant component of the treatment agent adheres firmly to the fiber and becomes glued. After drying, it is set and the dimensions are stabilized. Iron at the appropriate temperature of the fiber and finish the wrinkles and stretched parts. In addition, when acid treatment or reduction treatment is performed, a specified amount of acid or a reducing agent is added to the anti-shrink treatment or treatment solution. However, in the case of using a fiber that has been previously treated with a polyvalent metal salt, acid treatment, or reduction treatment, it is not necessary to add an oxidizing agent or a reducing agent. Note that pilling resistance is improved by performing a reduction treatment with hydroxyalkylphosphine.
[0059]
In the case of a knitted fabric that requires processing sequence and shrinkage, the shrinkage treatment is first performed on the knitted fabric. Thereafter, reduction / oxidation treatment is performed to cleave the cuticle (scale) portion on the hair surface and the disulfide bond in the C, M, and C portions, and the —S—S— bond is converted to —SH. Thereafter, washing with water is performed and the process proceeds to a shrinkage-preventing step.
[0060]
Next, a shrinking treatment is performed. First, an object to be processed is put into a solution in which an anti-shrinkable component consisting of components A to E, F component, and G component are dissolved, and the mixture is slowly stirred to perform the treatment. When texture adjustment is required, processing is performed by adding a part of the F component and G component after the processing. Then, it wash | cleans with water and complete | finishes a process.
[0061]
The shrink-proof component of the treatment agent of the present invention is dispersed in water in the form of a minute water-containing gel or micelle. In the immersion liquid or in the wet stage, some of the shrinkage-resistant components adhere firmly to the fiber, but a part of the shrink-proof component merely adheres to the fiber. The reason why it adheres firmly to the fiber is that after the moisture has been volatilized, the fine gels and micelles have been destroyed, and some of the active ingredients of the treatment agent of the present invention have been deposited and adhered to the water-swelling fiber. . Therefore, if strong centrifugal dehydration is performed at the time of dehydration, or if the water content is reduced to 20% by weight or less due to excessive squeezing, the shrink-proof component flows out together with water, and the expression of the shrink-proof effect is weak.
[0062]
Then, the water treatment of the fiber after a shrink-proof process and the washing method are demonstrated. Usually, wool and other animal hair fibers are crimped and felt in about 10 to 60 seconds under intense friction such as hand-gripping in an aqueous solution containing a detergent for clothing such as sodium dodecylbenbensulfonate. . In addition, when using a washing machine for textiles with a dry cleaning label based on a polyethylene alkyl ether nonionic surfactant as a main component, if a household washing machine is used, wash for 3 to 5 minutes. It is described that the water washing is finished by rinsing for a minute.
[0063]
The fiber product of animal hair such as wool treated with the treatment agent of the present invention exhibits a resistance of 10 minutes or more even under intense friction such as hand squeezing in a liquid to which the above-mentioned detergent for clothing is added, and further oxidation / reduction treatment When it is used, it shows resistance for 15 minutes or more. In the untreated blank, curing starts in about 15 seconds and felting occurs. Further, the treated cloth is resistant to shrinkage for 60 minutes or more even if it is washed using a household washing machine and added with a detergent for sodium dodecylbenzenesulfonate.
[0064]
The effect of using a nitrogen-containing surfactant alone having 6 or more carbon atoms in the alkyl group of the F component is as follows. Coconut oil fatty acid diethanolamide, lauric acid diethanolamide, ethyl sulfate lanolin fatty acid aminopropylethyldimethylammonium chloride, distearyldimethylammonium chloride, polyoxyethylene lauryl ether sulfate triethanolamine, alkyl (11,13,15) triethanolamine sulfate, Coconut oil fatty acid amidopropyl betaine solution was used, but no shrink-proof effect was produced. However, a slight delay effect of felting is recognized, and resistance to around 45 seconds is exhibited even under intense friction such as hand-grip described later. In addition, the alkyl group having 6 or more carbon atoms of the F component attached by the combined use with the A to E components and the G component of the present invention exhibits hydrophobicity, and has a shrinkage-preventing effect by inhibiting water from entering the hair. It seems that it was accepted.
[0065]
The effect of using the aliphatic aldehyde compound and / or aromatic aldehyde compound alone as the G component is as follows.
Glutaraldehyde, a water-soluble aliphatic aldehyde with little discoloration (Germany, BASF trade name: Relugan) was used, but no shrink-proof effect was observed. However, the effect was recognized by using together with the A to E components of the present invention. This is presumed to be due to crosslinking of the A to F and H components from the fibers by crosslinking with the treating agent component.
[0066]
The effects of using an oxidizing agent and a reducing agent alone are as follows.
Although monooxyphthalic acid and monopersulfate were used as oxidizing agents at pH 3-4, and sodium metasuccinate, sodium carbonate, sodium thiosulfate, and sodium sulfite were used as reducing agents in the range of PH 8-12. I was not able to admit. When trishydroxypropylphosphine is used alone as the reducing agent and anti-pilling agent, the treated cloth is cured and the texture is lowered, but shrinkage resistance is recognized immediately after the treatment. However, when water washing was repeated, there was a considerable decrease in shrinkage resistance. The pilling prevention effect increased as the amount added increased. However, when used in combination with the treatment agent of the present invention, effects of improving texture, maintaining shrinkage resistance, and anti-pilling were observed. Trishydroxypropylphosphine showed similar anti-pilling properties even when the amount used was reduced when an enzyme (protease system) was used in combination. However, only the enzyme (protease system) was added in a small amount and did not show an anti-pilling effect. When the amount of the enzyme added is increased, it is difficult to manage the work process, it is expensive, and the strength of the animal hair fiber is reduced. These are thought to be due to weakening of the hydrophobicity / hydrophobicity of the animal hair surface, increasing the amount attached to the fiber surface and adhering, and reducing the rise of the cuticle (scale).
[0067]
The method of carrying out the shrink-proof treatment and washing at the same time in one liquid is as follows. When performing the laundering method of the test cloth described later, the specified amount of the anti-shrinkage treatment agents A to G of the present invention is poured simultaneously with the detergent for washing. In addition, the fiber product shrunk by wearing can be extended and restored to a new length.
[0068]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. Various test methods performed in these Examples and Comparative Examples are as follows.
[0069]
○ Fiber shrinkage rate: compliant with JIS-L-1042 method and test method for shrinkage rate of fabric.
[0070]
○ Shrinkage rate of knitting: (1) Conforms to JIS-L-1081 · 1990, knitted fabric test method 6.30G method (household electric washing machine method).
{Circle around (2)} Conforms to JIS-L-1057, iron shrinkage test method for woven and knitted fabrics, and B-1 method (steaming iron method).
The length of the measurement section before and after the treatment, which is a basis for calculating the shrinkage ratio when the treatment with the shrink-proofing treatment agent of the present invention and water washing, and water washing is repeated, is obtained by treating the fiber cloth with this treatment agent. It calculated using the numerical value before doing. The shrinkage was calculated according to the following formula.
Shrinkage rate = (length of measurement section before processing−length of measurement section after processing) / length of measurement section before processing × 100
If the shrinkage rate is negative, it indicates elongation.
[0071]
O Washing test: Conforms to JIS-L-0217, display symbols and handling methods for textile products, test methods for separate symbols, numbers 103 and 105.
[0072]
○ Pilling test: JIS-L-1076, woven and knitted pilling test method A method (method using ICI type tester).
[0073]
○ Texture: The feel of each processed product when the unprocessed product is set to “no change” was compared in five stages (decrease, slightly decrease, no change, slightly improve, improve).
[0074]
○ Hand washing test
Put the cloth to be washed in an aqueous solution containing detergent (Kao, 20g of attack standard water 30 liters), roll the cloth in the hands of both hands, and then strongly compress the cloth in the hand. Rotated vigorously and rubbed quickly to wash it. After scrubbing, take out every 20 seconds, lightly pull the crispy cloth, correct the wrinkled stretch and deformed parts, and then measure the vertical and horizontal dimensions. Repeat this for 180 seconds of hand-washing. In an untreated fabric of knitting, rapid shrinkage is usually seen in 10 to 60 seconds. In the case of a highly shrinkable fabric, complete felting occurs after 40 seconds. After 60 to 80 seconds, the knitted treated cloth shows substantially the same shrinkage as the shrinkage rate after 10 times of laundering laundering in a household electric washing machine is repeated. The knitted fabric used was 10 × 10 (cm). In a normal knitted fabric, when it is immersed in water, a relaxation stress works and shrinkage of 2 to 10% occurs. Or the shrinkage is different in the vertical and horizontal (wale / course) and deforms. When the shrinkage of the knitted fiber is less than 6% in the longitudinal and transverse lengths, it can be easily restored by pulling for crease stretching. With a shrinkage of 6-10%, it can be restored by pulling with a slight force. In the case of shrinkage of 10 to 19%, if a force is applied and pulling is performed, the original size can be restored. However, if shrinkage of more than 25% occurs, felting occurs and the restoration is difficult. The degree of shrinkage (easy to do) can be determined in a short time by this hand washing test. As a result of the hand kneading test, an electric washing machine was washed for those having a small shrinkage rate to determine the chemicals to be used, the amount of addition, and the resistance to water washing. If the elongation is large, it can be easily restored to its original dimensions by spraying steam and cooling it.
[0075]
Table 2 shows the blending ratios of the F component, G component, H component: reducing agent, etc. with the A to E components of the shrink-proofing agent used for the test cloth test being 100% by weight.
[0076]
[Table 2]

[0077]
The detail of the composition component of Table 2 is as follows.

[0078]
The details of the used H component: reducing agent and ripening agent are as follows.
Reducing agent (1): Mixture of 4 parts of sodium sulfite, 2 parts of sodium thiosulfate and 1 part of sodium carbonate
Reducing agent (2): Trishydroxypropylphosphine (Nippon Chemical Industry, Pyrgon PP-40) anti-pilling agent
Reducing agent (3): Enzyme, O, W, F, 0.3% added (Nippon Kagaku Kogyo, Enzain WS; main component protease system)
(Note) The enzyme was used because the anti-pilling effect was observed even when the amount of trishydroxypropylphosphine added was decreased.
Shrinking agent (1): Kao Corporation Emar 40
Shrinking agent (2): Sanyo Chemical Industries, Ltd. Sandet ADX
[0079]
The shrink-proof treatment method of the test cloth is as follows. .
Processing order
(1) Shrinkage treatment (implemented for knitting that requires shrinkage)
(2) Reduction treatment (implemented for those requiring reduction treatment)
In addition, the thing which requires anti-pilling property was processed using trishydroxypropylphosphine.
(3) Shrink-proof treatment (A to G components were used)
[0080]
[Trimping treatment]
A specified amount: bath ratio (multiple of the amount of diluted water per weight of the object to be treated, hereinafter the same) is injected with 1:30 hot water at 50 ° C., and Table 2 frying agents O, W, F (weight of object to be treated) 6-8% and the detergent (Kao Attack) 1% were added to obtain a uniform solution. An object to be treated was put into this liquid, immersed for 20 to 30 minutes, slowly stirred, drained, and washed with water.
[0081]
[Reduction treatment]
It implemented with respect to the to-be-processed object which has not been oxidized / reduced beforehand. In Table 2, those treated with reducing agent (1) alone and those treated with reducing agent (1) and then treated with reducing agent (2) (some of which are added with the enzyme shown in reducing agent (3)), Three types of tests were carried out for those treated with the reducing agent (2) alone, and the anti-pilling properties were mainly compared.
[0082]
Warm water at 50 ° C. was poured into the treatment tank at a bath ratio of 1:30, and the reducing agent (1) in Table 2 was added in an amount of 4 to 6% as O, W, and F to obtain a uniform liquid. An object to be treated was put into this liquid, immersed for 20 to 30 minutes, slowly stirred, drained, and washed with water.
[0083]
[Providing anti-pilling properties]
The test was conducted with trishydroxypropylphosphine alone and with enzyme. The results showed that the same effect was obtained when the enzyme (main component protease) was used in combination even if the amount of trishydroxypropylphosphine added was small. The enzyme alone did not improve the anti-pilling property. Table 3 shows the compounding ratio and anti-pilling property of the drug when trishydroxypropylphosphine and an enzyme are used. Cashmere knitting was used as the treated fabric.
[0084]
[Table 3]

[0085]
Table Description Examples 37 to 40, Comparative Example 10
50 ° C. warm water was added to the treatment tank at a bath ratio of 1:30, and the chemicals shown in Table 3 were added to obtain a uniform solution. Cashmere knitting was put in, immersed for 30 minutes, slowly stirred, washed with water after draining. When an enzyme was added, an organic acid having a pH of 3 or less was added to deactivate the enzyme, and then the solution was removed and washed with water. Thereafter, the pilling property was tested after the shrink-proof treatment.
[0086]
[Shrinkproof treatment]
40 degreeC warm water was inject | poured into the processing tank in the ratio of 1-30 bath ratio. A to E components in Table 2 are added as O, W, F 6%, F component palm oil fatty acid diethanolamide 4%, and G component 2% to obtain a uniform solution. The material to be treated was added and slowly stirred, and after 10 minutes, 2% of the F component quaternary ammonium salt type cationic surfactant was added. After 10 minutes, the liquid was removed and washed with water. It dehydrated to about 30% water content with a centrifuge. When wet and wet, the dimensions of the object to be processed measured in advance were compared, and when it was stretched and deformed, the tension was corrected and dried. Or, after drying, steam was blown to correct the shape of the fiber.
[0087]
Tables 4 to 5 show the shrinkage ratios of cashmere knitted products after water rinsing after treatment with the treatment agent.
[0088]
[Table 4]

[0089]
Explanation of Table 4
Cashmere knitting test, Examples 1 to 13 and Comparative Example 1 were blank (untreated)
1. Test cloth: 100% cashmere, a cloth immediately after knitting by a flat knitting machine was used.
2. Shrinkage rate (1) JIS-L-1081G method, values after 10 washes, according to the Tokyo Metropolitan Textile Industry Laboratory report.
(2) Hand-washing test: Calculated by the average value of shrinkage in the wale direction and the course direction.
(3) In accordance with the JIS-L-0217.105 law, using a household electric washing machine, put it in a washing net, extend the washing time, perform washing, perform "rinse" every 30 minutes, and measure the dimensions did. This was repeated three times. 90 minutes after washing JIS-L-1057. Processed according to the B-1 method, measured, and calculated by the average value of the shrinkage rate in the wale direction and the course direction.
3. Pilling test: Test values based on results from the Tokyo Textile Industry Laboratory, Hair Products Inspection Association, Japan Chemical Fiber Inspection Association, and Japan Spinning Inspection Association were used.
4). (Used drugs): The types of contraction agent, the combination of reducing agents, and the types of components A to H used the drugs shown in the component details of Table 2.
[0090]
[Table 5]

[0091]
Description of Table 5 Cashmere knit laundry shrinkage Example 14
Test cloth: The test cloth of Example 5 was used. Agent used: Same as in Example 5.
Test method: JIS-L-1018-1990 Knitted fabric test method 6.30G method (household electric washing machine method)
However, it is based on the test method specified in the attached table of JIS-L-0217 (Indicating Symbols for Handling of Textile Products and Their Dimensional Indicating Methods) and (1) Washing Method No. 105 in Test Methods by Symbols.
Drying: Screen drying. Detergent: Neutral Akron was used. In the test, “washing, drying, and measurement” were repeated 10 times for the same material, and the shrinkage was calculated based on the initial length each time.
(Note) The test values based on the results from the Tokyo Textile Industry Laboratory were used.
[0092]
[Table 6]

[0093]
Description of Table 6 Examples 15 to 19 and Comparative Example 2 were blank (untreated).
1. Test fabric: 100% wool, wool yarn knit, flat knitted fabric
2. Shrinkage rate (1) Hand-washing test: It was calculated by the average value of the shrinkage rate in the wale direction and the course direction.
(2) Using a household electric washing machine, in accordance with JIS-L-0217,105, put it in the washing net, extend the washing time, perform washing, and perform "rinse" every 30 minutes. Measured. This was repeated three times. In addition, it processed according to JIS-L-1057, B-1 direction after 90 minutes washing, measured, and calculated by the average value of the shrinkage | contraction rate of a wale direction and a course direction.
3. (Used drug): The combination of components A to H used the drugs shown in the component specifications of Table 2.
[0094]
[Table 7]

[0095]
Description of Table 7 Examples 20 to 26 and Comparative Example 3 were blank (untreated).
1. Test cloth: Thick knitted cloth by twill knitting using spun yarn by wool and Angola blend
2. Shrinkage rate: (1) Hand-washing test
▲ 2 ▼ Home electric washing machine test
The same shrinkage test method and calculation method as shown in Table 6 were used.
3. (Used drugs): The combinations of components A to H used the drugs shown in the component specifications of Table 2.
[0096]
[Table 8]

[0097]
(Explanation of Table 8)
1. Knit products used for testing
Shrinkage after washing of knitted products
Knit (1): Cashmere 100% flat knitted sweater Weight 250g
Knit (2): 100% wool wool yarn sweater Weight 480g
Knit (3): 100% woolen woolen sweater Weight 280g
Knit (4): 80% wool 20% mohair 20% woolen yarn sweater Weight 675g
[0098]
2. Drugs used in test products and treatment methods
The treatments of Examples 27 to 30 were the same as the chemicals used in Example 13 and the treatment method.
[0099]
3. Washing method
(1) Compliant with JIS-L-0217-105 method (washing an electric machine, using a washing net).
(2) For the second wash, use a product sweater after the first wash, and in accordance with the JIS-L-0217-105 method (use of a laundry net), the wash time is extended and 30 minutes of continuous washing is performed. did.
(3) For the third wash, continuous washing for 30 minutes was performed using the product sweater after the second wash as in the second wash.
(4) Since the product sweater is rinsed, shrinks after dehydration, and has many wrinkles, it is stretched with wrinkles and stretched after being dehydrated, stretched into wrinkles, folded in half, and then dried by drying. It was.
[0100]
4). Shrinkage
(1) About the product sweater after washing and drying, the dimensions of the body length, the width of the garment (upper and lower arm), the width of the garment (lower and hem), the length of the sleeve, and the width of the sleeve end were measured and entered.
(2) The dimensions before washing were measured and filled in by measuring the dimensions after shrinkage treatment and drying.
(3) The dimensions before the treatment were filled in by measuring the dimensions of the product sweater before the shrink-proof treatment.
(4) The dimensions after finishing are measured after the third time (60 minutes) after washing and drying, the dimensions are corrected by blowing steam and hot air on the sweater, and the dimensions are measured after cooling. Filled in.
(Note) Since the sweater after washing for 60 minutes has not been felted, it easily stretches when pulled. Moreover, the dimensions could be corrected more easily by spraying steam.
[0101]
[Table 9]

Description of Table 9 Shrinkage of fabric after washing
1. Used fabric cloth
Although it was a woven fabric, it was tested mainly on fabrics that were easily stretched when pulled like a knitted fabric, and contracted and deformed when immersed in water, and that were difficult to handle during sewing.
(1) Normal dimension: A value measured in a normal condition (when left at room temperature, the same applies hereinafter) as a standard for easily expanding and contracting was defined as “normal dimension”.
(2) Normal tensile dimension: Measured in the normal state as pulled and stretched to obtain a “normal tensile dimension”.
(3) Dimensions before washing (after treatment): The test cloth contracted due to relaxation stress.
In the comparative example: After immersing in only warm water at 35 ° C. for 15 minutes, the dimensions were measured and filled in after drying.
In the examples: a shrink-proof treatment was performed using an untreated cloth that was not immersed in water, and the dimensions were measured and filled in after drying.
[0102]
(4) Types of test cloth
Cloth-1: 100% wool twisted yarn (1600 times / m) Stretchable thin woven cloth Co., Ltd. Toshi Hanai
Cloth-2: 100% wool strong twisted yarn (1600 times / m) Stretchable thin densely woven cloth manufactured by Toshi Hanai
Cloth-3: Wool strong twisted yarn, stretchable thick ground coarse woven fabric, manufactured by Toshi Hanai
Cloth-4: Wool 90% Nylon 10%
Cloth-5: 100% wool striped twill weave made by Toshi Hanai
[0103]
2. Chemicals used for the treatment of test cloth and treatment method
Comparative Examples 4 to 7 were blanks, and a chemical treatment was not performed using a cloth dipped only in the warm water described above.
Examples 31 to 35 were the same as the drugs used and the treatment method of Example 13.
[0104]
3. Washing method (1) Conforms to JIS-L-0217-105 method (electric machine washing machine washing).
(2) For the second washing, the cloth after the first washing was used, and in accordance with the JIS-L-0217-105 method, only the washing time was extended and continuous washing for 30 minutes was performed.
(3) In the third wash, the cloth after the second wash was used for 30 minutes of continuous washing as in the second wash.
[0105]
4). Shrinkage factor
(1) Using the cloth after washing and rinsing and drying, the vertical and horizontal dimensions were measured and calculated from the difference from the normal dimensions.
(2) The cloth tested this time has stretchability, or there was a cloth with a smaller shrinkage rate in the next round than in the previous round. Was obtained.
[0106]
[Table 10]

[0107]
(Explanation of Table 10) Shrinkage after fur (mouton) washing
1. Test fur: Sheepskin with a wool length of 23 mm (chrome tanning)
20cm x 20cm (70g) x 2 sheets
[0108]
2. Types of treatment agents
I. Table 2 Anti-shrink components (100%) composed of A to E of composition 3 were used.
B. Table 2 125% F component was used.
C. Table 2 33% G component was used.
D. Table 2 H component reducing agent and 133% anti-pilling agent were used.
(Note) Comparative Example-9 was blank and no treatment was performed.
[0109]
3. Drug processing sequence and dimensions
(1) A to E components: O, W, F 3%, bath ratio 1:30, mouton was immersed in a 30 ° C. bath, stirred for 10 minutes, rested for 50 minutes, and immersed for a total of 5 hours.
(2) H component reducing agent 2, anti-pilling agent: O, W, F 10%, dibasic sodium phosphate heptahydrate 2 g / liter, nonionic surfactant 1%, bath ratio 1:30, in liquid for 30 minutes After soaking the mouton, the solution was drained and washed with water.
(3) O, W, F: G component 2%, F component 6%, A to E component 3%, bath ratio 1:30, immersed in 30 ° C. solution for 30 minutes, then drained and washed with water.
[0110]
4). Washing method (electric washing machine washing)
(1) Conforms to JIS-L-0217-105 method (use of laundry net)
(2) For the second time, fur (mouton) after the first washing was used, and in accordance with the JIS-L-0217-105 method, only the washing time was extended and continuous washing for 30 minutes was performed.
(3) In the third washing, 30 minutes of continuous washing was performed using the fur (mouton) after the second washing in the same manner as in the second washing.
[0111]
5). Shrinkage factor
(1) Using the fur (mouton) after washing, rinsing and drying, the vertical and horizontal dimensions were measured and calculated from the difference from the dimensions before the treatment.
(2) Rate of change: shows the change in dimensions due to treatment with a shrink-proofing agent.
(3) The dimensions before the treatment were used as the dimensions for the shrinkage rate and change rate.
[0112]
【The invention's effect】
As described above, according to the present invention, even if the water treatment time is extended for animal hair products, etc., or the number of times of water washing is increased, the shrinkage-preventing effect can be maintained. Has pilling properties. Accordingly, animal hair products and the like treated according to the present invention have the feature that dimensional stability, flexibility, texture, etc. are improved because crimping and felting are delayed even after repeated water treatment and washing. In addition, the shrinkage rate can be reduced even for products such as knitted fabrics with coarse stitches and strong twisted woven fabrics that are easily shrunk only by being immersed in water. Furthermore, animal hair products and the like treated according to the present invention are washed repeatedly by adding detergent to tap water, and even if they are exposed to direct sunlight and dried, there is little fuzzing, little change in appearance, flexibility, dimensional stability Not only loses pills, but also has excellent effects such as no change in properties such as pilling resistance, mechanical strength, bending resistance, wear resistance, moderate heat retention, moisture retention, breathability, moisture absorption and desorption Can play.

Claims (5)

As an anti-shrink component,
A component: 2 to 6 functional polyalkylene oxide polyol is 5 to 80% by weight,
Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6 functional polyalkylene oxide polyol,
Component C: 5-94.7% by weight of water-soluble polyurethane and / or water-dispersible polyurethane,
Component D: 0.1 to 7% by weight of 2 to 4 metal salt,
E component: Surfactant (however, excluding nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group) is 0.1 to 20% by weight,
(However, the sum of A component + B component + C component + D component + E component is 100% by weight)
For 100% by weight of the shrink-proof component,
F component: 20 to 200% by weight of a nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms,
G component: Aliphatic aldehyde compound and / or aromatic aldehyde compound 5 to 100% by weight
A solid or liquid animal hair fiber product and animal leather product shrink-proofing agent comprising As an anti-shrink component,
A component: 2 to 6 functional polyalkylene oxide polyol is 5 to 80% by weight,
Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6 functional polyalkylene oxide polyol,
Component C: 5-94.7% by weight of water-soluble polyurethane and / or water-dispersible polyurethane,
Component D: 0.1 to 7% by weight of 2 to 4 metal salt,
E component: Surfactant (however, excluding nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group) is 0.1 to 20% by weight,
(However, the sum of A component + B component + C component + D component + E component is 100% by weight)
For 100% by weight of the shrink-proof component,
F component: 20 to 200% by weight of a nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms,
G component: Aliphatic aldehyde compound and / or aromatic aldehyde compound 5 to 100% by weight
It is characterized by delaying felting of animal hair fiber products or animal leather products by immersing animal hair fiber products or animal leather products for a certain period of time in a solid or liquid shrink-proofing agent comprising A method for preventing shrinkage of animal hair fiber products and animal leather products. As an anti-shrink component,
A component: 2 to 6 functional polyalkylene oxide polyol is 5 to 80% by weight,
Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6 functional polyalkylene oxide polyol,
Component C: 5-94.7% by weight of water-soluble polyurethane and / or water-dispersible polyurethane,
Component D: 0.1 to 7% by weight of 2 to 4 metal salt,
E component: Surfactant (however, excluding nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group) is 0.1 to 20% by weight,
(However, the sum of A component + B component + C component + D component + E component is 100% by weight)
For 100% by weight of the shrink-proof component,
F component: 20 to 200% by weight of a nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms,
G component: Aliphatic aldehyde compound and / or aromatic aldehyde compound 5 to 100% by weight,
H component: hydroxyalkylphosphine 50 to 300% by weight
A solid or liquid animal hair fiber product and animal leather product shrink-proofing agent comprising As an anti-shrink component,
A component: 2 to 6 functional polyalkylene oxide polyol is 5 to 80% by weight,
Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6 functional polyalkylene oxide polyol,
Component C: 5-94.7% by weight of water-soluble polyurethane and / or water-dispersible polyurethane,
Component D: 0.1 to 7% by weight of 2 to 4 metal salt,
E component: Surfactant (however, excluding nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group) is 0.1 to 20% by weight,
(However, the sum of A component + B component + C component + D component + E component is 100% by weight)
For 100% by weight of the shrink-proof component,
F component: 20 to 200% by weight of a nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms,
G component: Aliphatic aldehyde compound and / or aromatic aldehyde compound 5 to 100% by weight,
H component: hydroxyalkylphosphine 50 to 300% by weight
By immersing and attaching animal hair fiber products or animal leather products for a certain period of time in a solid or liquid shrink-proofing agent comprising A method for preventing shrinkage of animal hair fiber products and animal leather products characterized by delaying the conversion. During the treatment process, an oxidizing agent or a reducing agent is added to oxidize or reduce animal hair fiber product or animal leather product fiber, or a polyvalent metal salt treatment or oxidation / reduction treatment in advance. The hair fiber product or animal leather product is used, The shrinkage treatment method for animal hair fiber product or animal leather product according to claim 2 or 4 .