JP4002440B2 - Mixed dyed product of disperse dyeable fiber and polyurethane fiber - Google Patents

Description

【００３７】
なお、式中、Ｒ_１及びＲ_２はそれぞれ炭素数２〜５のアルキル基を表し、Ｒ_３は炭素数１〜１０のアルキル基を表す。
【００３８】
上記の第３級窒素含有ジオール（Ａ）として好ましいものは、Ｎ−ブチル−ビス（２−ヒドロキシエチル）アミン、Ｎ−ブチル−ビス（２−ヒドロキシプロピル）アミン、Ｎ−ブチルビス（２−ヒドロキシブチル）アミン、Ｎ,Ｎ−ビス（２−ヒドロキシエチル）−イソブチルアミン、Ｎ,Ｎ−ビス（２−ヒドロキシプロピル）−イソブチルアミン、Ｎ,Ｎ−ビス（２−ヒドロキシブチル）−イソブチルアミン、Ｎ,Ｎ−ビス（２−ヒドロキシエチル）−ｔ−ブチルアミン、Ｎ,Ｎ−ビス（２−ヒドロキシプロピル）−ｔ−ブチルアミン、Ｎ,Ｎ−ビス（２−ヒドロキシブチル）−ｔ−ブチルアミン、Ｎ,Ｎ−ビス（２−ヒドロキシエチル）−１,１−ジメチルプロピルアミン、Ｎ,Ｎ−ビス（２−ヒドロキシプロピル）−１,１−ジメチルプロピルアミン、Ｎ,Ｎ−ビス（２−ヒドロキシブチル）−１,１−ジメチルプロピルアミンなどである。
【００３９】
上記の有機ジイソシアネート（Ｂ）として好ましいものは、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネートや３−メチルヘキサン−１,６−ジイソシアネート及び３−３′−ジメチルペンタン−１,５−ジイソシアネートの様な分岐構造を持つジイソシアネートをはじめ１,３−及び１,４−シクロヘキシレン−ジイソシアネートや４−４′−メチレンジシクロヘキシル−ジイソシアネートの様な環状脂肪族ジイソシアネート、ｍ−及びｐ−キシリレンジイソシアネート及びα,α,α′,α′−テトラメチル−ｐ−キシリレンジイソシアネートの様な芳香脂肪族ジイソシアネートなどである。
【００４０】
上記の共重合ポリウレタン化合物は、一般的にはＮ,Ｎ−ビス（ヒドロキシアルキル）−アルキルアミン化合物（Ａ）と有機ジイソシアネート（Ｂ）のうち、（Ａ）、（Ｂ）の少なくとも一方を２種以上含む反応系で共重合反応させることによって得られる。
【００４１】
上記のウレア化合物とは、（ａ）第１級アミン及び第２級アミンの内の少なくとも一種から選ばれる２官能性アミノ基と第３級窒素及び複素環状窒素の内の少なくとも一種から選ばれる窒素含有基とを含む窒素含有化合物と、（ｂ）有機ジイソシアナート、（ｃ）モノ又はジアルキルモノアミン、アルキルモノアルコール、有機モノイソシアナートの群から選ばれる少なくとも１種の化合物、とを反応させて得ることができるものである。得られるウレア化合物には活性末端が残らないように、上記の（ａ）、（ｂ）、（ｃ）のモル当量比を調整の上、反応させることが重要である。得られるウレア化合物は、下記の化２で示される第３級窒素骨格と、化３、化４で示されるウレア結合を含む。但し、アルキルモノアルコールを反応させた場合は、化５で示されるウレタン結合も含む。
【００４２】
【化２】

【００４３】
【化３】

【００４４】
【化４】

【００４５】
【化５】

【００４６】
また、ウレア化合物は、化合物（ｃ）の選択によって、化２〜化５の構造を満足する下記の２種類の構造、化６と化７に分類される。
【００４７】
【化６】

【００４８】
【化７】

【００４９】
なお、構造中のｎは１以上の重合繰り返し数を表す。
【００５０】
化合物（ｃ）がモノ又はジアルキルモノアミン又はアルキルモノアルコールの場合は、化６であり、（ｃ）が有機モノイソシアナートの場合は、化７である。より好ましい構造としては、化７で示される（ｃ）が有機モノイソシアナートの場合である。
【００５１】
この２種類の構造を持つウレア化合物は、単独使用が好ましいが、混合して用いることもできる。
【００５２】
上記のウレア化合物を得るのに使用される化合物（ａ）の、第１級アミン及び第２級アミンの内の少なくとも一種から選ばれる２官能性アミノ基と第３級窒素及び複素環状窒素の内の少なくとも一種から選ばれる窒素含有基とを含む窒素含有化合物としては、Ｎ−ブチル−ビス（２−アミノエチル）アミン、Ｎ−ブチル−ビス（２−アミノプロピル）アミン、Ｎ−ブチル−ビス（２−アミノブチル）アミン、Ｎ,Ｎ−ビス（２−アミノエチル）−イソブチルアミン、Ｎ,Ｎ−ビス（２−アミノプロピル）−イソブチルアミン、Ｎ,Ｎ−ビス（２−アミノエチル）−ｔ−ブチルアミン、Ｎ,Ｎ−ビス（２−アミノエチル）−１,１−ジメチルプロピルアミン、Ｎ,Ｎ−ビス（２−アミノプロピル）−１,１−ジメチルプロピルアミン、Ｎ,Ｎ−ビス（２−アミノブチル）−１,１−ジメチルプロピルアミン、Ｎ−（Ｎ,Ｎ−ジエチル−３−アミノプロピル）−ビス（２−アミノエチル）アミン、Ｎ−（Ｎ,Ｎ−ジブチル−３−アミノプロピル）−ビス（２−アミノプロピル）アミン、ピペラジン、ピペラジン誘導体、例えば２−メチルピペラジン、１−（２−アミノエチル）−４−（３−アミノプロピル）ピペラジン、２,５−および２,６−ジメチルピペラジン、Ｎ,Ｎ’−ビス（２−アミノエチル）ピペラジン、Ｎ,Ｎ’−ビス（３−アミノプロピル）ピペラジン、Ｎ−（２−アミノメチル）ピペラジン、Ｎ−（２−アミノエチル）ピペラジン、Ｎ−アミノ−（２−アミノエチル）−４−メチルピペラジン等、ピペリジン誘導体、例えば４−アミノエチルピペリジン、Ｎ−アミノ−４−（２−アミノエチル）ピペリジン、Ｎ−ビス（２−アミノエチル）アミン−ピペリジン等、ピロリドン誘導体、例えばＮ−アミノ−４−（２−アミノエチル）−２−ピロリドン、Ｎ−（３−アミノプロピル）−４−（３−アミノプロピル）−２−ピロリドン、Ｎ−ビス（２−アミノエチル）アミン−２−ピロリドン等が挙げられる。好ましい窒素含有化合物は、ピペラジン、ピペラジン誘導体である。特に、得られるウレア化合物のアミド系溶媒への溶解性が極めて良好であるＮ−（２−アミノエチル）ピペラジン、Ｎ−（２−アミノプロピル）ピペラジンが好適である。これらは単独であるいは混合して用いることができる。
【００５３】
上記のウレア化合物を得るのに使用される（ｂ）の有機ジイソシアナートとしては、トリメチレンジイソシアナート、テトラメチレンジイソシアナート、ペンタメチレンジイソシアナート、ヘキサメチレンジイソシアナート、３−メチルヘキサン−１,６−ジイソシアナート、３,３’−ジメチルペンタン−１,５−ジイソシアナート、１,３−及び１,４−シクロヘキシレン−ジイソシアナート、４,４’−ジシクロヘキシルメタン−ジイソシアナート、ｍ−及びｐ−キシリレンジイソシアナート、α,α,α’,α’−テトラメチル−ｐ−キシリレンジイソシアナート、４,４’−ジフェニルメタン−ジイソシアナート、イソホロンジイソシアナート、２,４−トリレンジイソシアナート等が挙げられる。好ましくは、イソホロンジイソシアナート、４,４’−ジシクロヘキシルメタン−ジイソシアナートのような脂環族ジイソシアナートがよい。これらは単独であるいは混合して用いることができる。
【００５４】
上記のウレア化合物を得るのに使用される化合物（ｃ）のモノ又はジアルキルモノアミンとしては、炭素数１〜１０のアルキル基を有するモノアミンであり、例えば、イソプロピルアミン、ｎ−ブチルアミン、ｔ−ブチルアミン、ジエチルアミン、２−エチルヘキシルアミン、ジイソプロピルアミン、ジ−ｎ−ブチルアミン、ジ−ｔ−ブチルアミン、ジ−イソブチルアミン、ジ−２−エチルヘキシルアミン等が挙げられる。また、アルキル鎖中に第３級窒素原子や酸素原子を含んでいてもよく、例えば、３−ジブチルアミノ−プロピルアミン、３−ジエチルアミノ−プロピルアミン、３−エトキシプロピルアミン、３−（２−エチルヘキシルオキシ）プロピルアミンが挙げられる。これらは単独であるいは混合して用いることができる。
【００５５】
上記のウレア化合物を得るのに使用される化合物（ｃ）のアルキルモノアルコールとしては、炭素数１〜１０のアルキル基を有するモノアルコールであり、例えば、メタノール、エタノール、２−プロパノール、２−メチル−２−プロパノール、１−ブタノール、２−エチル−１−ヘキサノール、３−メチル−１−ブタノール等が挙げられる。これらは単独であるいは混合して用いることができる。上記のモノ又はジアルキルアミンとアルキルアルコールはそれぞれ単独で、あるいは混合して用いることができる。好ましくは単独での使用である。
【００５６】
さらに上記のウレア化合物を得るのに使用される化合物（ｃ）の有機モノイソシアナートとしては、ｎ−ブチルイソシアナート、フェニルイソシアナート、１−ナフチルイソシアナート、ｐ−クロロフェニルイソシアナート、シクロヘキシルイソシアナート、ｍ−トリルイソシアナート、ベンジルイソシアナート、ｍ−ニトロフェニルイソシアナート等が挙げられる。これらは単独で、あるいは混合して用いることができる。但し、前述のモノ又はジアルキルアミン、アルキルアルコールとの混用はできない。モノ又はジアルキルアミン、アルキルアルコールの活性水素を有機モノイソシアナートが封鎖した化合物が生成し、化６又は化７の構造をもつウレア化合物の有効量が減少するばかりでなく、該化合物はポリウレタンウレア弾性繊維の加工工程においてブリードアウトして、編み機や染色浴槽を汚すスカムの原因となるからである。
【００５７】
上記のウレア化合物を得るのに使用される化合物（ｃ）は、前述の如く３種から選択され、化合物（ａ）と化合物（ｂ）から得られるウレア化合物の活性末端（アミノ基又はイソシアナート基）を封鎖する。この活性末端はポリウレタンウレア弾性繊維の紡糸安定性を悪化させたり、堅牢度を低下させる。反応モル当量が（ａ）＞（ｂ）の場合にはウレア化合物末端がアミノ基であるために化合物（ｃ）は有機モノイソシアナートを選択し、（ａ）＜（ｂ）の場合にはウレア化合物末端がイソシアナート基であるため（ｃ）はモノ又はジアルキルアミンとアルキルモノアルコールの少なくとも一種を選択するする必要がある。好ましくは前記したように有機モノイソシアナートを選択することである。
【００５８】
上記のウレア化合物は、下記の化８及び化９で示されるウレア結合単位を１分子中に平均４〜４０個含む。ここで平均とは数平均のことである。
【００５９】
【化８】

【００６０】
【化９】

【００６１】
化合物（ｃ）がモノ又はジアルキルモノアミン又はアルキルモノアルコールの場合、ウレア化合物の構造は、下記の化１０で示される。
【００６２】
【化１０】

【００６３】
なお、構造中のｎは１以上の重合繰り返し数を表す。
【００６４】
所望の平均ウレア結合単位数を持つウレア化合物は、化合物（ａ）、（ｂ）及び（ｃ）の反応仕込みモル比を調整することで得られる。すなわち、（ａ）：（ｂ）：（ｃ）＝ｎ：（ｎ＋１）：２となるように調整すれば、１分子中に存在する平均ウレア結合単位数はモノ又はジアルキルモノアミンでは２ｎ＋２、アルキルモノアルコールでは２ｎとなる。
【００６５】
（ｃ）が有機モノイソシアナートの場合、ウレア化合物の構造は、下記の化１１で示される
【００６６】
【化１１】

【００６７】
なお、構造中のｎは１以上の重合繰り返し数を表す。
【００６８】
このとき（ａ）：（ｂ）：（ｃ）＝（ｎ＋１）：ｎ：２となるように調整すれば、１分子中に存在する平均ウレア結合単位数は２ｎ＋２となる。
【００６９】
上記のウレア化合物は、１分子中に存在する平均ウレア結合単位数が、好ましくは４〜４０の範囲である。構造中の重合繰り返し数ｎに換算すれば、モノ又はジアルキルモノアミン、有機モノイソシアナートの場合は１〜１９、アルキルモノアルコールでは２〜２０である。平均ウレア結合単位数が４〜４０であると、十分な熱セット性が得られる。また、平均ウレア結合単位数が少なすぎると、ポリウレタンウレア弾性繊維の加工工程においてブリードアウトして編機や染色浴槽を汚すスカムの原因となる場合がある。さらに、平均ウレア結合単位数が多すぎると、ウレア化合物がポリウレタンウレア紡糸原液中で析出し紡糸糸切れが生じたり、ポリウレタンウレア弾性繊維の伸度の低下が起こり弾性機能が損なわれる傾向がある。より好ましい平均ウレア結合単位数はウレア化合物の１分子中に４〜１５である。
【００７０】
次に、下記の化１２で示される化合物も、上記でいう３級窒素化合物である。
【００７１】
【化１２】

【００７２】
なお、式中、Ｘは下記の化１３又は化１４で示される基であり、Ｙ_１、Ｙ_２、Ｙ_３、Ｙ_４のうち少なくとも３つは下記の化１５で示される基であり、他の基が存在する場合にはこの基はグリシジル誘導体基である。
【００７３】
【化１３】

【００７４】
【化１４】

【００７５】
【化１５】

【００７６】
Ｒ_１、Ｒ_２はアルキル基又はアルアルキル基であって、Ｒ_１とＲ_２のうち少なくとも１つは１級炭素により化１５の窒素原子と結合しており、Ｒ_１とＲ_２の炭素数の合計は４以上である。またＺは下記の化１６で示される基が少なくとも３個存在するものである。
【００７７】
【化１６】

【００７８】
なお、式中、Ｒ_３、Ｒ_４は同一または相異なる炭素数１〜４のアルキル基を示す。
【００７９】
上記の化１２で示される具体的化合物については、特公平２−３４９８５号公報に記載の方法により製造することができる。
【００８０】
さらに、（ＣＨ_３）_３−Ｃ−なる反復単位と、下記の化１７で表される反復単位とからなる第３級窒素含有ポリマーをもつ化合物も、上記でいう３級窒素化合物である。
【００８１】
【化１７】

【００８２】
なお、式中、Ｒ_１は炭素数２〜６のアルキレン基を示し、Ｒ_２とＲ_３は同一又は相異なる炭素数１〜６のアルキル基を示す。
【００８３】
このイソブチレン単位とマレイミド単位よりなるポリマーは、イソブチレンと無水マレイン酸とのポリマーに、ＮＨ_２−Ｒ_１−Ｎ（Ｒ_２）（Ｒ_３）なるアミンを反応せしめることによって容易に得ることができる（なお、Ｒ_２とＲ_３は同一又は相異なる炭素数１〜６のアルキル基を示す）。具体的には特公平３−６１７７号公報に記載の方法により得ることができる。
【００８４】
本発明において、混用されるポリウレタン繊維には、上述の３級窒素化合物が含まれており、３級窒素化合物は単独又は二種以上含まれていてもよく、その含有量は、好ましくは０．１〜１５ｗｔ％である。この範囲であると、本発明の目的が十分に達成され、添加したことによる効果が有効に得られるので、優れた糸物性が得られるのみならず経済的である。
【００８５】
なお、３級窒素化合物をポリウレタン重合体に添加する方法は、特に限定されず、例えば、ポリウレタンの重合前、重合中もしくは重合後に混合する。
【００８６】
本発明の分散染料可染型繊維に混用するポリウレタン繊維の割合は、用途により適宜決めることができるが、おおむねポリウレタン繊維を４０ｗｔ％以下混用させた場合に好ましい結果が得られる。また、本発明の混用染色品は分散染料可染型繊維とポリウレタン繊維とからなるが、この両繊維以外に、ウール、絹、麻等を混用しても構わない。
【００８７】
本発明の混用染色品の形態としては、糸条形態と布帛形態に大別される。
【００８８】
糸条形態としては、ポリウレタン繊維の裸糸（１０〜５００ｄｔｅｘ）に分散染料可染型繊維を被覆した糸条、例えば、いわゆるカバリングヤーン（シングル並びにダブルカバリング）、合撚糸、コアヤーン、交絡糸等、公知の被覆糸の形態が挙げられる。
【００８９】
又、布帛形態としては、編物、織物、不織布並びにこれらの複合布帛（例えば、積層布等）がある。具体例としては、いわゆる機上混用品があり、製編織時に、ポリウレタン繊維の裸糸（裸糸の場合は編成や製織時、２〜４倍程度に伸長させながら）又は被覆糸を機上にて分散染料可染型繊維と引き揃えて、又は合糸して混用した編織物が挙げられる。
【００９０】
本発明において、混用の形態については何ら制限されるのものではなく、分散染料可染型繊維とポリウレタン繊維が公知の混用手段によって混用されていればよい。
【００９１】
本発明の混用染色品は、ＪＩＳ Ｌ−０８４４ Ａ−２法における洗濯堅牢度が３〜４級以上であって、ＪＩＳ Ｌ−０８６０法におけるドライクリーニング液汚染が３級以上であることが好ましい。この範囲であると、各種用途において問題なく使用可能である。
【００９２】
本発明の混用染色品を得る方法は、上記のような混用品を分散染料と金属錯塩染料を用いて染色し、分散染料で染色後にアルカリ還元洗浄をすることに特徴がある。
【００９３】
分散染料としては、通常のベンゼンアゾ系染料のみならず、アルカリ易加水分解性染料であるジエステル基を有する分散染料、アゾ系分散染料の中でもチアゾール型、チオフェン型が良好であり、ベンゾジフラノン型分散染料、アルキルアミン基を有する分散染料などが挙げられるが、特に分解生成物の着色のないものが好ましい。特に、アルカリ易加水分解性染料を用いた場合、アルカリ還元洗浄によりポリウレタン繊維中の分散染料を選択的に除去しやすいので、堅牢度性能が良好となる。
【００９４】
金属錯塩染料としては、遷移金属と染料よりなる錯体が、負電荷を有する色素アニオンのソーダ塩の構造を有する水溶性の染料であることが好ましく、遷移金属としてはクロムやコバルト等が例示される。遷移金属と染料との比率は、例えば、１：１、１：２が挙げられるが、好ましくは１：２型を用いるのが好ましい。但し、１：２型金属錯塩染料においては、分散型、スルホアミド型は分散染料可染型繊維への汚染が大きく、堅牢度性能が劣る傾向にある。一方、硫酸基を有するモノスルホネート型、ジスルホネート型は、還元洗浄により、分散染料可染型繊維に付着した染料の除去性が良好であり、染色品の色の安定性、堅牢度性能が良好なことからより好ましい。
【００９５】
また、ポリウレタン繊維への金属錯塩染料の染着性は、本発明でいう３級窒素化合物との親和性に基づくものであり、３級窒素化合物の含有量が多いほど染着性は良好となる。さらに３級窒素化合物と金属錯塩染料との親和性が高いことから、染色後のアルカリ浴での還元洗浄を実施しても還元洗浄耐久性が４０％以上と高く、しかも色相変化がないことから、目むき対策として有用であり、堅牢度性能も良好である。
【００９６】
還元洗浄耐久性は、１３０℃で３０分染色後のポリウレタン繊維の発色性をＫ／Ｓ値にて測定し、還元洗浄（二酸化チオ尿素２ｇ／リットル、苛性ソーダー２ｇ／リットルを使用して８０℃で２０分間処理）後のポリウレタン繊維の発色性をＫ／Ｓ値にて測定し、次式により還元洗浄耐久性を求めた。
【００９７】
還元洗浄耐久性（％）＝｛（還元洗浄後のＫ／Ｓ値）／（還元洗浄前のＫ／Ｓ値）｝×１００
金属錯塩染料の染料濃度は６％ｏｍｆ未満であることが好ましい。ポリウレタン繊維に金属錯塩染料を染着させることで目むき対策を行うことから、染料濃度６％ｏｍｆ以上を用いても、染料の使用量に見合うだけの効果は得られず不経済である。
【００９８】
本発明において、分散染料と金属錯塩染料により染色する方法は、分散染料と金属錯塩染料を同浴で用いて染色する１浴１段染色法や、金属錯塩染料で前記の混用品を先に染色し、その後、分散染料で染色する２浴法が挙げられる。
【００９９】
１浴法にて染色する場合の染色条件は、ポリエステル繊維等に通常適用される、分散染料による染色条件が適用される。すなわち染色浴としては、染料の他に分散均染剤、ｐＨ調整剤等を含んだ染料液を用いて、１００〜１３５℃の温度のもとで２０〜４０分間染色を行う。
【０１００】
２浴法にて、金属錯塩染料を先に染色する場合には、ポリアミド繊維やウール等に通常適用されている染色条件を適用すればよい。
【０１０１】
本発明においては、いずれの染色法を採用した場合も、分散染料で染色後に、アルカリ浴での還元洗浄を実施することが、堅牢度性能に優れた混用染色品を得るうえで重要である。
【０１０２】
アルカリ浴での還元洗浄条件は、ポリエステル繊維に通常適用されている条件であればよく、例えば、アルカリ成分としては苛性ソーダやソーダ灰などが、また還元剤としてはハイドロサルファイト、二酸化チオ尿素、ロンガリットＣ（ナトリウムスルホキシレートホルムアルデヒド）、ロンガリットＣＬ、ロンガリットＺなどを使用すればよい。この際アルカリ成分の濃度及び還元剤の濃度は、各々１〜１０ｇ／リットルが好ましい。
【０１０３】
また、繊維膨潤剤として一般に使用されているキャリヤー、例えば、クロルベンゼン系、メチルナフタリン系、オルソフェニルフェノール系、芳香族エーテル系、芳香族エステル系などを０．５〜５ｇ／リットル併用してもかまわない。さらに、ポリウレタン繊維に親和性があるポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレンアルキルフェノールエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアミンエーテル、ポリオキシエチレンアルキルベンジルアンモニウムクロライド、アルキルピコリウムクロライドなどを、０．５〜５ｇ／リットル併用してもかまわない。還元洗浄の温度は特に限定されないが、４０〜９０℃の範囲が好ましく、処理時間は１０〜４０分が好ましい。
【０１０４】
上記のようにして分散染料と金属錯塩染料で染色された混用染色品は、分散染料で染色後のアルカリ浴での還元洗浄により、ポリウレタン繊維中の分散染料が除去され、金属錯塩染料は前記の３級窒素化合物と結合しているため、脱落量が比較的少なく、しかも色相変化がなく、ポリウレタン繊維の色は分散染料可染型繊維と同系色の色を保持している。このように、本発明により、発色性が高く、目むきがなく、染色堅牢度に優れた品質のよい分散染料可染型繊維とポリウレタン繊維との混用染色品が得られる。
【０１０５】
本発明においては、さらに好ましくは、分散染料で染色するに際し、多価金属化合物とタンニン酸で処理した後、染色すること（染色前の処理法）、あるいは染色する際に多価金属化合物とタンニン酸を併用すること（併用染色法）により、分散染料が、ポリウレタン繊維へ染着することを著しく抑制し、分散染料可染型繊維に選択的に染着するので、優れた発色性、染色堅牢度を有する分散染料可染型繊維とポリウレタン繊維との混用染色品が得られる。
【０１０６】
このような方法により、分散染料の構造タイプを問わずあらゆる分散染料において、ポリウレタン繊維への分散染料の染着を著しく低減させることができるので、アルカリ還元洗浄時のポリウレタン繊維中の分散染料除去を容易に行うことができ、ポリウレタン繊維への分散染料汚染問題に関わる堅牢度の問題を一挙に解決することが可能である。
【０１０７】
但し、ポリウレタン繊維としてポリエステルエーテル弾性繊維を用いた場合には、染色時にタンニン酸と多価金属化合物を含む染色浴で染色を行っても、ポリエステルエーテル弾性繊維への分散汚染抑制効果は認められない。
【０１０８】
ここで多価金属化合物としては、アンチモン系化合物が好ましいが、その他としてはスズ、アルミニウム、亜鉛、バリウム、ビスマス系化合物を用いることができ、これら多価金属化合物を併用して用いてもよい。
【０１０９】
アンチモン系化合物としては、酒石酸アンチモン塩が好ましく、酒石酸アンチモンナトリウム、酒石酸アンチモンカリウムが例示され、酒石酸アンチモンナトリウムが特に好ましく適用できる。
【０１１０】
多価金属化合物の使用量は、好ましくは０．０１〜１．５％ｏｍｆ、さらに好ましくは０．０２〜０．５％ｏｍｆである。この範囲であると、多価金属化合物の使用による効果が発揮されて、本発明の目的が十分に達成され、コスト面でも経済的である。
【０１１１】
タンニン酸としては、五倍子または没食子から得たタンニンが好ましく、その使用量は、製品濃度で好ましくは０．１〜１０％ｏｍｆ、さらに好ましくは０．２〜５％ｏｍｆである。この範囲であると、タンニン酸の使用による効果が発揮されて、本発明の目的が十分に達成され、コスト面でも経済的である。
【０１１２】
多価金属化合物とタンニン酸の使用量の比率は、１：１〜１：４０が好ましく、より好ましい比率は１：３〜１：２０であり、さらに好ましい比率は１：３〜１：１０である。
【０１１３】
前述した染色前の処理法は、多価金属化合物とタンニン酸を含有する水溶液中に本発明に用いる混用品を浸漬する方法が好ましく、処理温度としては４０〜１３０℃が好ましく、６０〜１００℃がより好ましく、処理時間は１０〜４０分が好ましい。この際、処理溶液のｐＨを３〜５に、酢酸等のｐＨ調整剤にて調整しておくのが好ましい。
【０１１４】
前処理を施した混用品は、前述したように、分散染料と金属錯塩染料とで染色を行えばよい。
【０１１５】
分散染料の染色浴に前記多価金属化合物とタンニン酸類を共存させる併用染色法は、通常ポリエステル繊維に適用されている染色条件を用いればよく、染料水溶液中に多価金属化合物とタンニン酸を溶解させ、１００〜１３５℃の温度で２０〜４０分染色すればよい。この際の染料水溶液のｐＨは４〜５に、酢酸等のｐＨ調整剤で調整しておくのが好ましい。
【０１１６】
この際に併用する分散均染剤としては、β−ナフタリンスルホン酸ホルムアルデヒド縮合体のようなアルキルナフタリン系や多価アルコール脂肪酸エステルのポリアルキレンオキサイド付加物とその硫酸化物を用いるのが好ましい。
【０１１７】
本発明においては、分散染料で染色後のアルカリ還元洗浄条件は、ポリウレタン繊維への分散染料の染着量が少ないことから、還元洗浄における還元剤濃度、アルカリ剤濃度は各々２〜４ｇ／リットルの条件で十分であり、処理温度も高める必要がなく、還元洗浄条件の強化の必要がないことから、分散染料可染型繊維の発色性が低下することがなく、還元洗浄バッチごとの色のバラツキがほとんどない。
【０１１８】
分散染料の染色浴にタンニン酸と多価金属化合物を共存させた染色浴による処理は、分散染料のポリウレタン繊維への染着を抑制し、分散染料可染型繊維への分散染料の分配を促進する作用に着目した処理であり、分散染料のポリウレタン繊維への染着が著しく抑制されるばかりでなく、ポリウレタン繊維へ拡散した分散染料は染色後のアルカリ還元洗浄により速やかに分解され、ポリウレタン繊維中からほぼ完全に除去される。その結果、混用染色品の湿潤染色堅牢度は飛躍的に高くなり、ドライクリーニング液汚染が顕著に低減した混用染色品が得られる。また本発明によれば、分散染料可染型繊維への分散染料の染着率を高め、染料の無駄を低減して、発色性が高く、見栄えのよい混用染色品の調製が可能になるほか、染色バッチごとの色のバラツキを抑え、染色機の操業率を向上させるという効果もある。
【０１１９】
尚、分散染料と金属錯塩染料との同浴染色浴中に前記多価金属化合物とタンニン酸を共存させる併用染色法においても、分散染料のポリウレタン繊維への染着抑制効果は変わらずに発揮され、しかも、分散染料の構造タイプを問わずあらゆる分散染料においても染着抑制効果は変わらず発揮される。
【０１２０】
また、ポリウレタン繊維中に前記の３級窒素化合物が含有されているため、金属錯塩染料のポリウレタン繊維への染着に対する悪影響はほとんどない。従って、アルカリ還元洗浄後における混用染色品は、分散染料可染型繊維には分散染料が、ポリウレタン繊維には金属錯塩染料が染着しており、発色性が高く、目むきがなく、染色堅牢度に優れた品質のよい混用染色品である。
【０１２１】
尚、本発明に用いる分散染料可染型繊維とポリウレタン繊維との混用品が布帛の場合は、編成、製織後、リラックス精練してから、染色することが好ましい。精練は６０〜９８℃の温度で、できるだけ布帛をリラックスさせた状態で行うことが、布帛の伸縮回復性を高めるなどの理由から好ましい。なお、染色前に形態固定を行いたい場合は、１７０〜２００℃の温度で乾熱でプレセットを行えばよい。次に、還元洗浄後は、常法に従って仕上げればよいが、ファイナルセット温度はプレセット温度より１０℃以上低くし、１７０℃以下にてセットすると好ましい結果が得られる。
【０１２２】
【発明の実施の形態】
以下、本発明を実施例などによりさらに説明するが、本発明はこれら実施例などにより何ら限定されるものではない。
【０１２３】
なお、「部」は「ｗｔ部」を表し、測定法、評価法等は下記の通りである。
【０１２４】
（１）洗濯堅牢度
混用染色品について、ＪＩＳ Ｌ−０８４４ Ａ−２法に従って評価した。
【０１２５】
試験片の変褪色と添付白布片の汚染の程度を、それぞれ変褪色用グレースケール、汚染用グレースケールと比較して判定した。
【０１２６】
また、洗濯後の液汚染については、試験後の汚れ液を磁器容器（２０ｍｍ×４０ｍｍ×１０ｍｍ）に８ｃｃ採り、液汚染程度を、汚染用グレースケールと比較して、その色落ち度を判定した。
【０１２７】
色落ちの少ない良好なものを５級とし、順次、色落ちの大きいものを１級として判定した。
【０１２８】
（２）汗アルカリ堅牢度
混用染色品について、ＪＩＳ Ｌ−０８４８−Ａ法に準じてアルカリ性人工汗液を用いて評価した。
【０１２９】
試験片の変褪色と添付白布片の汚染の程度を、それぞれ変褪色用グレースケール、汚染用グレースケールと比較して判定した。
【０１３０】
（３）ドライクリーニング液の汚染
混用染色品について、ＪＩＳ Ｌ−０８６０に準じてドライクリーニング試験を実施した。
【０１３１】
ドライクリーニング液とドライクリーニング試験後の汚れ液を磁器容器（２０ｍｍ×４０ｍｍ×１０ｍｍ）に８ｃｃ採り、液汚染程度を、汚染用グレースケールと比較してその色落ち度を判定した。
【０１３２】
色落ちの少ない良好なものを５級とし、順次、色落ちの大きいものを１級として判定した。
【０１３３】
（４）発色性（Ｌ値）
混用染色品（布帛）の表面を、分光測色計（Ｋｏｌｌｍｏｒｇｅｎ社製、形式マクベスＭＳ−２０２０）を使用して、Ｌａｂ表色系におけるＬ値を測定した。Ｌ値は低い方が発色性が高い。
【０１３４】
（５）目むき
混用染色品（布帛）を引っ張ったときに見えるポリウレタン繊維の色を判定した。分散染料可染型繊維とほぼ同じ色相の場合を○とし（目むきとならない状態）、ポリウレタン繊維の色が赤味や黄味のように分散染料可染型繊維の色相と極端に違う場合を×（目むき状態）と判定した。
【０１３５】
（６）ηｓｐ／ｃの測定法
ηｓｐ／ｃは、ポリマーを９０℃でｏ−クロロフェノールの溶剤に１ｇ／デシリットルの濃度で溶解し、その後、得られた溶液をオストワルド粘度管に移して３５℃で測定し、下記式により算出した。
【０１３６】
ηｓｐ/ｃ＝（Ｔ／Ｔ_０）／Ｃ
式中、Ｔは試料溶液の落下時間（秒）、Ｔ_０は溶剤の落下時間（秒）、Ｃは溶液濃度（ｇ／デシリットル）を表す。
【０１３７】
（７）ポリウレタン繊維及びポリエステルエーテル弾性繊維の繊度（デシテックス）
２０℃、相対湿度６５％雰囲気下で、ポリウレタン繊維あるいはポリエステルエーテル弾性繊維を無緊張かつ無荷電で直線状に静置して放縮させる。その後、試料を１０００ｍｍの長さで切断したものを１０本合わせて秤量し、１００００ｍあたりの質量（ｇ）に換算し、その値を繊度（デシテックス）とする。
【０１３８】
〔実施例１〕
ηｓｐ／ｃ＝０．６５、ＴｉＯ_２の含有量０．４％のポリエチレンテレフタレートを紡糸温度２９０℃で紡出し、スピンテイクアップ方式にて巻取速度７２００ｍ／分で巻取り、５６ｄｔｅｘ／２４ｆの糸条を得た。この糸条は、易染性ポリエステル繊維に該当するものである（染料吸尽率＝９１％）。
【０１３９】
数平均分子量１７００のポリテトラメチレンエーテルグリコール１０００部と４,４’７−ジフェニルメタンジイソシアネート２３５．６部を、窒素ガス気流中８５℃にて２時間撹拌しつつ反応させて、イソシアネート基を両末端に持つ中間重合体を得た。次いで、室温に冷却した後、これに乾燥ジメチルホルムアミド１８５３部を加えて溶解した。別に、エチレンジアミン１９．９４部、ジエチルアミン３．１部を乾燥ジメチルホルムアミド１９２２部に溶解させておき、これに上記の中間重合体の溶液を室温で添加すると、混合溶液はすみやかに反応して、粘度２２００ポイズ（３０℃）のポリウレタン溶液が得られた。
【０１４０】
次に、１００ｇのＮ,Ｎ−ビス（２−ヒドロキシプロピル）−１,１−ジメチルプロピルアミン及び７９．３ｇのＮ−ブチル−ビス（２−ヒドロキシエチル）アミン及び１９８．７ｇのイソホロンジイソシアネート及び３７８ｇのＮ,Ｎ−ジメチルアセトアミド溶液を、乾燥窒素ガス中、室温で撹拌下に、触媒としてジブチル錫ジラウレート０．１５ｇを添加して、１時間撹拌後、系内を７０℃にし、さらに５時間反応させ、赤外スペクトルで反応溶液中に未反応のイソシアネート基の２２７０ｃｍ^−１における吸収が消失した事を確認してから反応を終了させた。得られた共重合ポリウレタン化合物の溶解性パラメータδは１０．８６であった。
【０１４１】
得られた共重合ポリウレタン化合物を３部、及び少量の青み剤を含む酸化チタン２部を上記のポリウレタン溶液に加えた後、均一に分散溶解した。この溶液を脱泡し、通常の乾式紡糸により３１１ｄｔｅｘのポリエーテル系ポリウレタン繊維を得た。得られたポリウレタン繊維の強伸度物性は優れたものであった。
【０１４２】
上記の易染性ポリエステル繊維とポリウレタン繊維を用い、通常の編成条件にて６コース・サテンネット編地（コース密度１７０ループ数／２．５４ｃｍ、ウエル密度４０ループ数／２．５４ｃｍ）を作製した（ポリウレタン繊維の混率は２３ｗｔ％）。
【０１４３】
次いで、拡布状で９０℃で精練リラックスした後、１９０℃でプレセットを行い、下記条件にて染色した。
【０１４４】
（染色条件）
分散染料；ダイアニックス ネービー ＵＮ−ＳＥ（２００）（ダイスタージャパン（株）製）：３．５％ｏｍｆ
金属錯塩染料；ラナシン ネービ− Ｓ−ＤＮＬ（ジスルホネート型染料、還元洗浄耐久性７１．９％、クラリアントジャパン（株）製）：２％ｏｍｆ
分散均染剤；ニッカサンソルトＲＭ−３４０（日華化学工業（株）製）：０．５ｇ／リットル
酢酸 ；０．５ｃｃ／リットル
酢酸ナトリウム；１ｇ／リットル
浴比； １：２０
染色温度、時間；１２０℃、３０分
染色完了後、染色機から染色残液を排出し、染色機に水を入れ、温度を７５℃まで昇温し、これに下記薬剤を添加し、下記の濃度に調整した。
【０１４５】
二酸化チオ尿素；２ｇ／リットル
苛性ソーダー；２ｇ／リットル
サンモールＲＣ−７００（非イオン洗浄剤；日華化学工業（株）製）；０．５ｇ／リットル
浴比； １：３０
この還元洗浄液で、染色品に７５℃、１５分間の還元洗浄を施し、残液を排出し、温湯および水により染色物を十分にすすぎ洗いを施した後、１６０℃、３０秒間の乾熱セットで仕上げた。
【０１４６】
得られた染色品の洗濯堅牢度、汗アルカリ堅牢度、ドライクリーニング液汚染目むきを評価した。結果を表１に示す。
【０１４７】
なお、得られた染色品のポリエーテル系ポリウレタン繊維は、易染性ポリエステル繊維とほぼ同等の紺色の色相をしていた。
【０１４８】
〔実施例２〕
実施例１と同様のプレセットした編物を用い、分散染料と金属錯塩染料の染色浴中に下記濃度のタンニン酸、酒石酸アンチモンナトリウムを併用して染色したこと以外は、実施例１と同様にして染色をおこなった。
【０１４９】
タンニン酸： ２．０％ｏｍｆ
酒石酸アンチモンナトリウム：０．２％ｏｍｆ
染色後は、実施例１と同様にして、還元洗浄を施し、仕上げた。
【０１５０】
得られた染色品の洗濯堅牢度、汗アルカリ堅牢度、ドライクリーニング液汚染、目むきを評価した。結果を表１に示す。
【０１５１】
なお、得られた染色品のポリエーテル系ポリウレタン繊維は、易染性ポリエステル繊維とほぼ同等の紺色の色相をしていた。
【０１５２】
〔比較例１〕
実施例１において、金属錯塩染料を用いずに分散染料のみで染色したこと以外は、実施例１と同様にして染色加工を施し、仕上げた。結果を表１に示す。
【０１５３】
以上の結果より、本発明の染色方法による染色品は、発色性が高く、目むきがなく、洗濯堅牢度も４級以上と著しく良好であり、ドライクリーニング液汚染の少ない（３級以上）、商品価値の高いものが得られたことが明らかである。
【０１５４】
これに対して、比較例１による染色品は、堅牢度性能は良好なものの、発色性が低く、ポリエーテル系ポリウレタン繊維が赤味をおびて、目むきがあり、商品価値の低いものであることが判明した。
【０１５５】
〔実施例３〕
実施例１で得られたポリウレタン溶液に、ｐ−クレゾールとジシクロペンタジエンの重付加体のイソブチレン付加物１．５ｗｔ％、Ｎ,Ｎ−ビス（２−ヒドロキシエチル）−ｔ−ブチルアミン２．５ｗｔ％、２−（２’−ヒドロキシ−３’,５−ジベンジル−フェニル）−ベンゾトリアゾール０．３ｗｔ％、ステアリン酸マグネシウム０．０５ｗｔ％、及びＮ−（２−アミノエチル）ピペラジン、４,４−ジフェニルメタンジイソシアナート、フェニルイソシアナート（モル比２：１：２）とからなる平均ウレア結合単位数が４のウレア化合物６ｗｔ％、及び実施例１で得られた共重合ポリウレタン化合物３ｗｔ％を加えた後、均一に分散溶解した。この溶液を脱泡して、通常の乾式紡糸により３３ｄｔｅｘのポリエーテル系ポリウレタン繊維を得た。
【０１５６】
次いで、ポリエチレンテレフタレート８４ｄｔｅｘ／３６ｆ（クラレ（株）製、ＳＮ−２０００）と上記で得られた３３ｄｔｅｘのポリウレタン繊維を、２．５倍にＳ方向に８００Ｔ／ｍで合糸追撚し、この糸を経糸（経糸密度１４０本／２．５４ｃｍ）、緯糸（緯糸密度１００本／２．５４ｃｍ）にそれぞれ用い、２／１の綾織物を調製した（ポリウレタン繊維の混率は９％）。
【０１５７】
得られた混用織物を、常法により糊抜き精練、リラックスをした後、２００℃でプレセットを行い、下記の条件にて染色した。
【０１５８】
（染色条件）
分散染料；ディスパーゾール ブラック ＸＦ（三井ＢＡＳＦ染料（株）製、ジエステル型分散染料）：１４％ｏｍｆ
金属錯塩染料；アイゼン オパール ブラック ニュ（モノスルホネート型染料、還元洗浄耐久性６２．６％、保土ヶ谷化学工業（株）製）：１％ｏｍｆ
分散均染剤；ニッカサンソルトＲＭ−３４０（日華化学工業（株）製）：０．５ｇ／リットル
酢酸；０．５ｃｃ／リットル
酢酸ナトリウム；１ｇ／リットル
浴比； １：２０
染色温度、時間；１３０℃、３０分
染色完了後、染色機から染色残液を排出し、染色機に水を入れ、温度を８０℃まで昇温し、これに下記薬剤を添加し、下記の濃度に調整した。
【０１５９】
二酸化チオ尿素；４ｇ／リットル
苛性ソーダー；４ｇ／リットル
サンモールＲＣ−７００（非イオン洗浄剤；日華化学工業（株）製）；０．５ｇ／リットル
浴比； １：３０
この還元洗浄液で、染色品に８０℃、２０分間の還元洗浄を施し、残液を排出し、温湯および水により染色物を十分にすすぎ洗いを施したのち１７０℃、３０秒間の乾熱セットで仕上げた。
【０１６０】
得られた染色品の洗濯堅牢度、汗アルカリ堅牢度、ドライクリーニング液汚染目むきを評価した。結果を表１に示す。
【０１６１】
なお、得られた染色品のポリエーテル系ポリウレタン繊維は、易染性ポリエステル繊維とほぼ同等の黒い色相をしていた。
【０１６２】
〔実施例４〕
実施例３と同様のプレセットした織物を用い、分散染料と金属錯塩染料の染色浴中に下記濃度のタンニン酸、酒石酸アンチモンナトリウムを併用して染色したこと以外は、実施例３と同様にして染色をおこなった。
【０１６３】
タンニン酸：１．０％ｏｍｆ
酒石酸アンチモンナトリウム：０．２５％ｏｍｆ
染色完了後、染色機から染色残液を排出し、染色機に水を入れ、温度を８０℃まで昇温し、これに下記薬剤を添加し、下記の濃度に調整した。
【０１６４】
二酸化チオ尿素；２ｇ／リットル
苛性ソーダー；２ｇ／リットル
サンモールＲＣ−７００（非イオン洗浄剤；日華化学工業（株）製）；０．５ｇ／リットル
浴比； １：３０
この還元洗浄液で、染色品に８０℃、２０分間の還元洗浄を施し、残液を排出し、温湯および水により染色品を十分にすすぎ洗いを施した後、１７０℃、３０秒間の乾熱セットで仕上げた。
【０１６５】
得られた染色品の洗濯堅牢度、汗アルカリ堅牢度、ドライクリーニング液汚染、目むきを評価した。結果を表１に示す。
【０１６６】
なお、得られた染色品のポリエーテル系ポリウレタン繊維は、易染性ポリエステル繊維とほぼ同等の黒い色相をしていた。
【０１６７】
〔比較例２〕
実施例３において、金属錯塩染料を用いずに分散染料のみで染色したこと以外は、実施例３と同様にして染色加工を施し、仕上げた。結果を表１に示す。
【０１６８】
以上の結果より、本発明の染色方法による染色品は、発色性が高く、目むきがなく、洗濯堅牢度も４級以上と著しく良好であり、ドライクリーニング液汚染の少ない（３級以上）、商品価値の高いものが得られたことが明らかである。
【０１６９】
これに対して、比較例２による染色品は、堅牢度性能は良好なものの、発色性が低く、ポリエーテル系ポリウレタン繊維が赤味をおびて、目むきがあり、商品価値の低いものであった。
【０１７０】
【表１】

【０１７１】
【発明の効果】
本発明によれば、今までには得られなかった、発色性が高く、目むきがなく、洗濯堅牢度に優れ、しかもドライクリーニング液汚染の極めて少ない分散染料可染型繊維とポリウレタン繊維との混用染色品が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a mixed dyed product of disperse dyeable fiber and polyurethane fiber, and a dyeing method thereof.
[0002]
[Prior art]
When dyed with a disperse dye, a disperse dye-dyeable fiber typified by polyethylene terephthalate fiber is dyed excessively on the polyurethane fiber. In addition to the low quality and poor appearance, there is a problem that the dyeing fastness of the dyed mixed fabric is significantly reduced. For this reason, it is necessary to remove the disperse dye excessively dye | stained to a polyurethane fiber by the reduction | restoration washing | cleaning of the dyed fabric.
[0003]
However, since it is difficult to sufficiently remove disperse dyes excessively dyed on polyurethane fibers by reduction washing, satisfactory dyeing fastness has not been obtained. There is also a problem with the fastness to dry cleaning of the dyed fabric. When the obtained dyed product is dry-cleaned, there is a problem that the dry-cleaning liquid becomes extremely dirty and white background or other fibers are back-contaminated. The cause of this dry cleaning liquid contamination is the disperse dye remaining in the polyurethane fiber, and the degree of the dry cleaning liquid contamination is almost proportional to the residual concentration of the disperse dye.
[0004]
For this reason, the reduction washing of the mixed dyeing dyed with the disperse dye is performed under severe conditions in which the concentration of the reducing agent and the alkali agent is higher than the normal concentration, for example, 10 g / liter each, and the processing temperature is 90 ° C. It is necessary to strengthen the reducing cleaning conditions such as higher. However, in a mixed knitted fabric with a high polyurethane fiber covering degree such as a covering yarn, even if the reduction cleaning conditions are strengthened, the disperse dye in the polyurethane fiber cannot be removed to a satisfactory level, The color developability of the disperse dyeable fiber is lowered, and the color variation between dyeing batches is increased.
[0005]
Therefore, as seen in JP-A-4-240277, as a disperse dye, dyeing with a dye that is easily decomposed by alkaline reduction washing, such as a heterocyclic azo, a condensation disperse dye, or a diester disperse dye, A method for easily removing the disperse disperse dye in the polyurethane fiber is used, and in particular, a method for improving the fastness to washing has been proposed.
[0006]
However, this method is effective in removing the disperse dye in the polyurethane fiber and can achieve high fastness, but the polyurethane fiber is colored by the decomposition product of the disperse dye such as yellowish or reddish. There is a problem. For this reason, when a fabric product is stretched when worn or the like, the polyurethane fiber having a different color is visible, so that a so-called blinding phenomenon appears and the product value of the product is remarkably lowered.
[0007]
Therefore, in reality, a satisfactory blended fabric of disperse dyeable fiber and polyurethane fiber having high color developability, no discoloration, and excellent dyeing fastness has not been obtained.
[0008]
[Problems to be solved by the invention]
The present invention has been made against the background of the above circumstances, and is a disperse dye-dyeable fiber that has high color developability even when dyed with disperse dyes, has no discoloration, and has excellent dyeing fastness. An object of the present invention is to provide a dyed fabric of a mixed fabric of polyurethane and polyurethane fibers, and a dyeing method thereof.
[0009]
[Means for Solving the Problems]
As a result of intensive studies, the present inventor has come to make the present invention.
[0010]
That is, the present invention is as follows.
[0011]
1. Disperse dyeable fiber and polyurethane fiber mixed dyed product, disperse dyeable fiber dyed with disperse dye, and polyurethane fiber dyed with metal complex dye A mixed dyed product of disperse dyeable dyeable fiber and polyurethane fiber.
[0012]
2. 2. The disperse dyestuff according to the above 1, wherein the fastness to washing in the JIS L-0844 A-2 method is 3 to 4 or more, and the dry cleaning liquid contamination in the JIS L-0860 method is 3 or more. Mixed dyed product of dyed fiber and polyurethane fiber.
[0013]
3. 3. The mixed dyed article comprising the disperse dyeable dyeable fiber according to 1 or 2 above and a polyurethane fiber, wherein the polyurethane fiber contains a tertiary nitrogen compound.
[0014]
4). It is characterized in that a mixed product of disperse dyeable fiber and polyurethane fiber is dyed by a one-bath method or a two-bath method using a disperse dye and a metal complex dye, and is subjected to alkali reduction washing after dyeing with a disperse dye. A method for producing a mixed dyed product of disperse dyeable fiber and polyurethane fiber.
[0015]
Hereinafter, the present invention will be described in detail.
[0016]
In the present invention, the disperse dyeable fiber means a fiber dyeable with disperse dyes such as polyethylene terephthalate, polyoxyethylene benzoate, polybutylene terephthalate, polytrimethylene terephthalate, polyvinyl alcohol, and acetate.
[0017]
The disperse dyeable fiber preferably has a single yarn decitex of 0.1 to 6 dtex, more preferably 0.5 to 3 dtex, and a total decitex of 10 to 280 dtex. When such a fiber is used, a fabric excellent in dyeability and texture can be obtained.
[0018]
As the polyester fiber, it is preferable to use an easily dyeable polyester fiber in order to prevent thermal embrittlement of the polyurethane fiber. The readily dyeable polyester fiber is a disperse dye C.I. Disperse Blue 56 (CI Disperse Blue 56; for example, Resorin Blue FBL [manufactured by Dystar Co., Ltd.]), a dye usage amount of 3% omf, and a bath ratio. 50 times, pH 6 (adjusted with acetic acid), dispersant (for example, Disper TL [manufactured by Meisei Chemical Industry Co., Ltd.)] content 1 g / liter dyeing bath at 100 ° C. for 120 minutes, then dyed on fiber Refers to a fiber having an exhaustion rate of the dye of 80% or more.
[0019]
Here, the exhaustion rate of the dye is represented by the following equation.
[0020]
Dye exhaustion rate (%) = {[Amount of dye dyed on fiber (mass)] / [Amount of dye added to dye bath (mass)]} × 100
Such an easily dyeable polyester fiber is substantially made of polyethylene terephthalate, for example, spun at a spinning speed of 4000 m / min or more, and subjected to heat treatment at 220 to 300 ° C. with dry heat or 180 to 240 ° C. with wet heat. Examples thereof include a fiber made of a polyethylene terephthalate homopolymer and a so-called high speed spun fiber of a spin take-up type spun at a spinning speed of 6200 m / min or more. In addition, a linear polymer having ethylene terephthalate as a repeating unit, which is obtained by copolymerizing isophthalic acid, sodium salt of sulfonated isophthalic acid, polyethylene glycol, adipic acid or the like as a third component, is usually a synthetic fiber. It may contain a matting agent, a stabilizer, an antistatic agent and the like added to the. Further, the degree of polymerization is not particularly limited as long as it is within a range having normal fiber forming properties.
[0021]
Moreover, a polytrimethylene terephthalate fiber is mentioned as an easily dyeable polyester fiber.
[0022]
As a characteristic of polytrimethylene terephthalate fiber, the strength is preferably 2 to 5 cN / dtex, more preferably 2.5 to 4.5 cN / dtex, and still more preferably 3 to 4.5 cN / dtex. The elongation is preferably 30 to 60%, more preferably 35 to 55%, and still more preferably 40 to 55%. The elastic modulus is preferably 30 cN / dtex or less, more preferably 10 to 30 cN / dtex, still more preferably 12 to 28 cN / dtex, and particularly preferably 15 to 25 cN / dtex. The elastic recovery rate at 10% elongation is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and most preferably 95% or more.
[0023]
In the present invention, the polytrimethylene terephthalate fiber means a polyester fiber having a trimethylene terephthalate unit as a main repeating unit, and the trimethylene terephthalate unit is preferably about 50 mol% or more, more preferably 70 mol% or more, and still more preferably. Means 80 mol% or more, most preferably 90 mol% or more. Accordingly, the total amount of other acid components and / or glycol components as the third component is preferably about 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, and most preferably 10 mol. % Of polytrimethylene terephthalate contained in the range of not more than%.
[0024]
Polytrimethylene terephthalate is synthesized by combining terephthalic acid or a functional derivative thereof with trimethylene glycol or a functional derivative thereof in the presence of a catalyst under appropriate reaction conditions. In this synthesis process, a suitable one or two or more third components may be added to form a copolyester, or a polyester other than polytrimethylene terephthalate such as polyethylene terephthalate or polybutylene terephthalate, nylon, Trimethylene terephthalate may be blended or compositely spun (sheath core, side-by-side, etc.).
[0025]
Regarding composite spinning, polytrimethyl as the first component, as exemplified in JP-B No. 43-19108, JP-A No. 11-189923, JP-A No. 2000-239927, JP-A No. 2000-256918, and the like. Using methylene terephthalate, as the second component, polyester or nylon such as polytrimethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, etc., was combined and spun into a side-by-side type or an eccentric seascore type arranged side by side or eccentrically. In particular, a combination of polytrimethylene terephthalate and copolymerized polytrimethylene terephthalate or a combination of two types of polytrimethylene terephthalate having different intrinsic viscosities is preferable. The two types of polytrimethylene terephthalate with different intrinsic viscosities, as exemplified in Fig. 2, are compound stretched into a side-by-side type where the joint surface is curved so that the low viscosity side wraps around the high viscosity side. It is particularly preferable because it has both the properties and bulkiness.
[0026]
The third component to be added includes aliphatic dicarboxylic acids (oxalic acid, adipic acid, etc.), alicyclic dicarboxylic acids (cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acids (isophthalic acid, sodium sulfoisophthalic acid, etc.), fat Aliphatic glycols (ethylene glycol, 1,2-propylene glycol, tetramethylene glycol, etc.), alicyclic glycols (cyclohexane dimethanol, etc.), and aliphatic glycols containing aromatics (1,4-bis (β-hydroxyethoxy) ) Benzene), polyether glycol (polyethylene glycol, polypropylene glycol etc.), aliphatic oxycarboxylic acid (ω-oxycaproic acid etc.), aromatic oxycarboxylic acid (p-oxybenzoic acid etc.) and the like. In addition, compounds having one or three or more ester-forming functional groups (benzoic acid or the like or glycerin or the like) can also be used within the range where the polymer is substantially linear.
[0027]
In addition, matting agents such as titanium dioxide, stabilizers such as phosphoric acid, ultraviolet absorbers such as hydroxybenzophenone derivatives, crystallization nucleating agents such as talc, easy lubricants such as aerosil, antioxidants such as hindered phenol derivatives, Flame retardants, antistatic agents, pigments, fluorescent brighteners, infrared absorbers, antifoaming agents and the like may be contained.
[0028]
Regarding spinning of polytrimethylene terephthalate fiber, for example, after obtaining an undrawn yarn at a winding speed of about 1500 m / min, a method of spinning at about 2 to 3.5 times, a spinning-twisting step were directly connected. Any of a straight drawing method (spin draw method), a high-speed spinning method (spin take-up method) with a winding speed of 5000 m / min or more may be employed.
[0029]
The form of the fiber may be long fiber or short fiber, and may be uniform or thick in the length direction. Also in the cross section, round shape, triangle shape, L shape, T shape, Y shape, W shape, It may be a polygonal type such as an eight-leaf type, a flat shape, or a dogbone type, a multi-leaf type, a hollow type, or an indeterminate type. Furthermore, the forms of the yarn include ring spun yarn, open-end spun yarn, etc., multifilament yarn (including extra fine yarn), sweet-twisted yarn to strong twisted yarn, mixed yarn, false twisted yarn (POY drawn false twisted yarn) Air injection processed yarn and the like.
[0030]
In addition, other fibers such as natural fibers represented by wool within the range of 30 wt% or less, within the range not impairing the object of the present invention, blended fibers (silospan, silofil, etc.), entangled mixed fibers (high shrinkage yarn) May be mixed by means such as two-ply air injection processing, etc.
[0031]
In the present invention, as the polyurethane fibers, polyether diols such as polytetramethylene glycol are used as diol components, aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate are used as diisocyanate components, and polyether diamines such as ethylenediamine are used as diamine components. 4,4'-diphenylmethane diisocyanate, etc. with polyurethane fiber, polyester diol composed of polycaprolactone, polyester composed of adipic acid / 1,6-hexanediol / neopentyl glycol, and aliphatic diol such as butanediol Polyester-based polyurethane fibers having the diisocyanate component as an aromatic diisocyanate can be appropriately selected and used depending on the application.
[0032]
In addition, bright yarns with high sharpness, semi-dial type with reduced gloss, and the like can be appropriately selected and used depending on the application. Such a type can be controlled by, for example, the amount of titanium oxide added.
[0033]
The polyurethane fiber may contain a chlorine water deterioration preventing agent such as a metal oxide or a metal hydroxide as necessary. For example, magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide Aluminum hydroxide, hydrotalcite compounds, etc. may be used alone or as a mixture of two or more. The addition amount is preferably 0.1 to 6.0 wt%. In addition, other known stabilizers, ultraviolet absorbers and the like may be contained.
[0034]
In the present invention, the polyurethane fiber preferably contains a tertiary nitrogen compound. The tertiary nitrogen compound is, for example, a copolymer polyurethane or urea compound shown below or a compound represented by the following chemical formula 12 or chemical formula 17.
[0035]
The copolymer polyurethane is, for example, a copolymer of a tertiary nitrogen-containing diol (A) represented by the following chemical formula 1 and an organic diisocyanate (B), and includes at least one of (A) and (B) A copolymer polyurethane containing two or more of them and having a solubility parameter (δ) of 10.8 <δ <11.0.
[0036]
[Chemical 1]

[0037]
In the formula, R ₁ And R ₂ Each represents an alkyl group having 2 to 5 carbon atoms; ₃ Represents an alkyl group having 1 to 10 carbon atoms.
[0038]
Preferred as the tertiary nitrogen-containing diol (A) is N-butyl-bis (2-hydroxyethyl) amine, N-butyl-bis (2-hydroxypropyl) amine, N-butylbis (2-hydroxybutyl). ) Amine, N, N-bis (2-hydroxyethyl) -isobutylamine, N, N-bis (2-hydroxypropyl) -isobutylamine, N, N-bis (2-hydroxybutyl) -isobutylamine, N, N-bis (2-hydroxyethyl) -t-butylamine, N, N-bis (2-hydroxypropyl) -t-butylamine, N, N-bis (2-hydroxybutyl) -t-butylamine, N, N- Bis (2-hydroxyethyl) -1,1-dimethylpropylamine, N, N-bis (2-hydroxypropyl) -1,1-dimethylpropylamine N, N-bis (2-hydroxybutyl) -1,1-dimethylpropylamine and the like.
[0039]
Preferred as the organic diisocyanate (B) are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 3-methylhexane-1,6-diisocyanate, and 3-3'-dimethylpentane-1,5. -Cyclic aliphatic diisocyanates such as diisocyanates having a branched structure such as diisocyanates, 1,3- and 1,4-cyclohexylene-diisocyanates and 4-4'-methylenedicyclohexyl-diisocyanates, m- and p-xylylene diene Isocyanates and araliphatic diisocyanates such as α, α, α ′, α′-tetramethyl-p-xylylene diisocyanate.
[0040]
The copolymer polyurethane compound is generally composed of at least one of (A) and (B) of N, N-bis (hydroxyalkyl) -alkylamine compound (A) and organic diisocyanate (B). It can be obtained by carrying out a copolymerization reaction in the reaction system including the above.
[0041]
The above urea compound means (a) a bifunctional amino group selected from at least one of primary amines and secondary amines, and nitrogen selected from at least one of tertiary nitrogen and heterocyclic nitrogen. A nitrogen-containing compound containing a containing group and (b) an organic diisocyanate, (c) at least one compound selected from the group consisting of a mono- or dialkyl monoamine, an alkyl monoalcohol, and an organic monoisocyanate, It can be obtained. It is important to carry out the reaction after adjusting the molar equivalent ratio of the above (a), (b), and (c) so that no active terminal remains in the resulting urea compound. The resulting urea compound contains a tertiary nitrogen skeleton represented by the chemical formula 2 below and a urea bond represented by the chemical formulas 3 and 4. However, when an alkyl monoalcohol is reacted, a urethane bond represented by Chemical Formula 5 is also included.
[0042]
[Chemical 2]

[0043]
[Chemical 3]

[0044]
[Formula 4]

[0045]
[Chemical formula 5]

[0046]
The urea compounds are classified into the following two types of structures satisfying the structures of Chemical Formulas 2 to 5 depending on the selection of the compound (c): Chemical Formula 6 and Chemical Formula 7.
[0047]
[Chemical 6]

[0048]
[Chemical 7]

[0049]
In addition, n in the structure represents a polymerization repeating number of 1 or more.
[0050]
When the compound (c) is a mono or dialkyl monoamine or an alkyl monoalcohol, the chemical formula 6 is obtained, and when the compound (c) is an organic monoisocyanate, the chemical formula 7 is designated. As a more preferred structure, (c) represented by Chemical Formula 7 is an organic monoisocyanate.
[0051]
These urea compounds having two types of structures are preferably used alone, but may be used in combination.
[0052]
Of the compound (a) used for obtaining the urea compound, a bifunctional amino group selected from at least one of a primary amine and a secondary amine, a tertiary nitrogen and a heterocyclic nitrogen are used. As a nitrogen-containing compound containing a nitrogen-containing group selected from at least one of N-butyl-bis (2-aminoethyl) amine, N-butyl-bis (2-aminopropyl) amine, N-butyl-bis ( 2-aminobutyl) amine, N, N-bis (2-aminoethyl) -isobutylamine, N, N-bis (2-aminopropyl) -isobutylamine, N, N-bis (2-aminoethyl) -t -Butylamine, N, N-bis (2-aminoethyl) -1,1-dimethylpropylamine, N, N-bis (2-aminopropyl) -1,1-dimethylpropylamine, N, N-bis (2 − Minobutyl) -1,1-dimethylpropylamine, N- (N, N-diethyl-3-aminopropyl) -bis (2-aminoethyl) amine, N- (N, N-dibutyl-3-aminopropyl)- Bis (2-aminopropyl) amine, piperazine, piperazine derivatives such as 2-methylpiperazine, 1- (2-aminoethyl) -4- (3-aminopropyl) piperazine, 2,5- and 2,6-dimethylpiperazine N, N′-bis (2-aminoethyl) piperazine, N, N′-bis (3-aminopropyl) piperazine, N- (2-aminomethyl) piperazine, N- (2-aminoethyl) piperazine, N Piperidine derivatives such as -amino- (2-aminoethyl) -4-methylpiperazine, such as 4-aminoethylpiperidine, N-amino-4- (2-aminoethyl) ) Pyrrolidone derivatives such as piperidine, N-bis (2-aminoethyl) amine-piperidine, such as N-amino-4- (2-aminoethyl) -2-pyrrolidone, N- (3-aminopropyl) -4- ( 3-aminopropyl) -2-pyrrolidone, N-bis (2-aminoethyl) amine-2-pyrrolidone and the like. Preferred nitrogen-containing compounds are piperazine and piperazine derivatives. In particular, N- (2-aminoethyl) piperazine and N- (2-aminopropyl) piperazine, which have very good solubility in the amide solvent of the resulting urea compound, are suitable. These can be used alone or in combination.
[0053]
As the organic diisocyanate (b) used to obtain the above urea compound, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 3-methylhexane 1,6-diisocyanate, 3,3′-dimethylpentane-1,5-diisocyanate, 1,3- and 1,4-cyclohexylene-diisocyanate, 4,4′-dicyclohexylmethane-di Isocyanate, m- and p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-p-xylylene diisocyanate, 4,4′-diphenylmethane-diisocyanate, isophorone diisocyanate, 2 , 4-tolylene diisocyanate and the like. Preferably, an alicyclic diisocyanate such as isophorone diisocyanate, 4,4′-dicyclohexylmethane-diisocyanate is used. These can be used alone or in combination.
[0054]
The mono- or dialkyl monoamine of the compound (c) used for obtaining the urea compound is a monoamine having an alkyl group having 1 to 10 carbon atoms, such as isopropylamine, n-butylamine, t-butylamine, Examples include diethylamine, 2-ethylhexylamine, diisopropylamine, di-n-butylamine, di-t-butylamine, di-isobutylamine, di-2-ethylhexylamine and the like. Further, the alkyl chain may contain a tertiary nitrogen atom or an oxygen atom, such as 3-dibutylamino-propylamine, 3-diethylamino-propylamine, 3-ethoxypropylamine, 3- (2-ethylhexyl). And oxy) propylamine. These can be used alone or in combination.
[0055]
The alkyl monoalcohol of the compound (c) used to obtain the above urea compound is a monoalcohol having an alkyl group having 1 to 10 carbon atoms, such as methanol, ethanol, 2-propanol, 2-methyl. Examples include 2-propanol, 1-butanol, 2-ethyl-1-hexanol, 3-methyl-1-butanol and the like. These can be used alone or in combination. The above mono- or dialkylamine and alkyl alcohol can be used alone or in combination. Preferably, it is used alone.
[0056]
Furthermore, as the organic monoisocyanate of the compound (c) used for obtaining the above urea compound, n-butyl isocyanate, phenyl isocyanate, 1-naphthyl isocyanate, p-chlorophenyl isocyanate, cyclohexyl isocyanate, m-Tolyl isocyanate, benzyl isocyanate, m-nitrophenyl isocyanate and the like can be mentioned. These can be used alone or in combination. However, it cannot be mixed with the aforementioned mono- or dialkylamine or alkyl alcohol. A compound in which an active hydrogen of a mono- or dialkylamine or alkyl alcohol is blocked with an organic monoisocyanate is generated, and not only the effective amount of the urea compound having the structure of Chemical Formula 6 or Chemical Formula 7 is decreased, but the compound has a polyurethane urea elasticity. It is because it causes scum which bleeds out in the fiber processing step and soils the knitting machine and the dyeing bathtub.
[0057]
The compound (c) used to obtain the above urea compound is selected from three types as described above, and the active terminal (amino group or isocyanate group) of the urea compound obtained from the compound (a) and the compound (b). ). This active terminal deteriorates the spinning stability of the polyurethaneurea elastic fiber and decreases the fastness. When the reaction molar equivalent is (a)> (b), since the urea compound terminal is an amino group, compound (c) selects an organic monoisocyanate, and when (a) <(b), urea is selected. Since the end of the compound is an isocyanate group, (c) needs to select at least one of mono- or dialkylamine and alkyl monoalcohol. Preferably, the organic monoisocyanate is selected as described above.
[0058]
The above urea compound contains an average of 4 to 40 urea binding units represented by the following chemical formulas 8 and 9 in one molecule. Here, the average is a number average.
[0059]
[Chemical 8]

[0060]
[Chemical 9]

[0061]
When the compound (c) is a mono or dialkyl monoamine or an alkyl monoalcohol, the structure of the urea compound is represented by the following chemical formula 10.
[0062]
Embedded image

[0063]
In addition, n in the structure represents a polymerization repeating number of 1 or more.
[0064]
A urea compound having a desired average number of urea bonding units can be obtained by adjusting the reaction charge molar ratio of the compounds (a), (b) and (c). That is, if adjusted so that (a) :( b) :( c) = n: (n + 1): 2, the average number of urea bond units present in one molecule is 2n + 2 for mono or dialkyl monoamines, alkyl mono With alcohol, it becomes 2n.
[0065]
When (c) is an organic monoisocyanate, the structure of the urea compound is represented by the following chemical formula 11.
[0066]
Embedded image

[0067]
In addition, n in the structure represents a polymerization repeating number of 1 or more.
[0068]
At this time, if the adjustment is made such that (a) :( b) :( c) = (n + 1): n: 2, the average number of urea bond units present in one molecule is 2n + 2.
[0069]
In the above urea compound, the average number of urea bond units present in one molecule is preferably in the range of 4 to 40. In terms of the number of polymerization repeats n in the structure, it is 1 to 19 in the case of mono- or dialkyl monoamines and organic monoisocyanates, and 2 to 20 in the case of alkyl monoalcohols. When the average number of urea bond units is 4 to 40, sufficient heat setting property is obtained. Moreover, when there are too few average urea bond units, it may cause the scum which bleeds out in the process of processing a polyurethane urea elastic fiber, and stains a knitting machine or a dyeing bathtub. Furthermore, if the average number of urea bond units is too large, the urea compound is precipitated in the polyurethane urea spinning dope, causing spun yarn breakage, or the elongation of the polyurethane urea elastic fiber is lowered, and the elastic function tends to be impaired. A more preferable average number of urea bond units is 4 to 15 in one molecule of the urea compound.
[0070]
Next, the compound represented by the following chemical formula 12 is also a tertiary nitrogen compound mentioned above.
[0071]
Embedded image

[0072]
In the formula, X is a group represented by the following chemical formula 13 or chemical formula 14; ₁ , Y ₂ , Y ₃ , Y ₄ At least three of them are groups represented by the following chemical formula 15, and when other groups are present, these groups are glycidyl derivative groups.
[0073]
Embedded image

[0074]
Embedded image

[0075]
Embedded image

[0076]
R ₁ , R ₂ Is an alkyl group or an aralkyl group, and R ₁ And R ₂ At least one of which is bonded to the nitrogen atom of Chemical Formula 15 by primary carbon, and R ₁ And R ₂ The total number of carbon atoms is 4 or more. Z is a group in which at least three groups represented by the following chemical formula 16 are present.
[0077]
Embedded image

[0078]
In the formula, R ₃ , R ₄ Are the same or different alkyl groups having 1 to 4 carbon atoms.
[0079]
About the specific compound shown by said Chemical formula 12, it can manufacture by the method as described in Japanese Patent Publication No. 2-34985.
[0080]
In addition, (CH ₃ ) ₃ A compound having a tertiary nitrogen-containing polymer composed of a repeating unit of -C- and a repeating unit represented by the following chemical formula 17 is also a tertiary nitrogen compound as described above.
[0081]
Embedded image

[0082]
In the formula, R ₁ Represents an alkylene group having 2 to 6 carbon atoms, and R ₂ And R ₃ Denote the same or different alkyl groups having 1 to 6 carbon atoms.
[0083]
This polymer comprising isobutylene units and maleimide units is a polymer of isobutylene and maleic anhydride. ₂ -R ₁ -N (R ₂ ) (R ₃ Can be easily obtained by reacting an amine ₂ And R ₃ Are the same or different alkyl groups having 1 to 6 carbon atoms). Specifically, it can be obtained by the method described in Japanese Patent Publication No. 3-6177.
[0084]
In the present invention, the above-described tertiary nitrogen compound is contained in the mixed polyurethane fiber, and the tertiary nitrogen compound may be contained alone or in combination of two or more, and the content thereof is preferably 0.00. 1 to 15 wt%. Within this range, the object of the present invention can be sufficiently achieved, and the effect of the addition can be obtained effectively, so that not only excellent yarn physical properties can be obtained, but also economical.
[0085]
The method for adding the tertiary nitrogen compound to the polyurethane polymer is not particularly limited. For example, the tertiary nitrogen compound is mixed before, during or after the polyurethane polymerization.
[0086]
The ratio of the polyurethane fiber to be mixed with the disperse dyeable fiber of the present invention can be appropriately determined depending on the use, but a preferable result is obtained when the polyurethane fiber is generally mixed in an amount of 40 wt% or less. The mixed dyed product of the present invention is composed of disperse dyeable fiber and polyurethane fiber, but in addition to these two fibers, wool, silk, hemp or the like may be mixed.
[0087]
The mixed dyed product according to the present invention is roughly classified into a yarn form and a fabric form.
[0088]
As the yarn form, a yarn in which a disperse dye-dyeable fiber is coated on a bare polyurethane yarn (10 to 500 dtex), for example, so-called covering yarn (single and double covering), twisted yarn, core yarn, entangled yarn, etc. The form of a well-known covering yarn is mentioned.
[0089]
Examples of the fabric form include knitted fabrics, woven fabrics, nonwoven fabrics, and composite fabrics thereof (for example, laminated fabrics). As a specific example, there is a so-called on-machine mixed article, and when knitting and weaving, the polyurethane fiber bare yarn (when knitting or weaving, it is stretched about 2 to 4 times) or coated yarn is put on the machine And knitted fabrics mixed with disperse dyeable dyeable fibers or mixed with yarns.
[0090]
In the present invention, the mixed form is not limited at all, and the disperse dyeable fiber and the polyurethane fiber may be mixed by a known mixing means.
[0091]
The mixed dyed product of the present invention preferably has a fastness to washing in the JIS L-0844 A-2 method of 3 to 4 or higher and a dry cleaning liquid contamination in the JIS L-0860 method of 3 or higher. Within this range, it can be used without problems in various applications.
[0092]
The method for obtaining the mixed dyed product of the present invention is characterized in that the above mixed product is dyed with a disperse dye and a metal complex dye, and is subjected to alkali reduction washing after dyeing with the disperse dye.
[0093]
As the disperse dye, not only a normal benzene azo dye, but also a disperse dye having a diester group which is an alkali hydrolyzable dye, among azo disperse dyes, thiazole type and thiophene type are good, benzodifuranone type disperse dye, Examples thereof include disperse dyes having an alkylamine group, and those having no decomposition products are particularly preferred. In particular, when an alkali easily hydrolyzable dye is used, the fastness performance is good because the disperse dye in the polyurethane fiber is easily selectively removed by alkali reduction washing.
[0094]
As the metal complex dye, a complex composed of a transition metal and a dye is preferably a water-soluble dye having a structure of a negatively charged pigment anion soda salt, and examples of the transition metal include chromium and cobalt. . The ratio between the transition metal and the dye is, for example, 1: 1 or 1: 2, but the 1: 2 type is preferably used. However, in the 1: 2 type metal complex dye, the disperse type and the sulfoamide type have a large contamination to the disperse dyeable fiber, and the fastness performance tends to be inferior. On the other hand, monosulfonate and disulfonate types having sulfate groups have good removal of dyes attached to disperse dyeable fibers by reduction washing, and color stability and fastness performance of dyed products are good. Therefore, it is more preferable.
[0095]
The dyeing property of the metal complex dye on the polyurethane fiber is based on the affinity with the tertiary nitrogen compound in the present invention, and the dyeing property becomes better as the content of the tertiary nitrogen compound increases. . Furthermore, since the affinity between the tertiary nitrogen compound and the metal complex dye is high, the reduction cleaning durability is as high as 40% or more and there is no hue change even if reduction cleaning in an alkaline bath after dyeing is performed. It is useful as a measure against blindness and has a good fastness performance.
[0096]
For reduction cleaning durability, color development of polyurethane fibers after dyeing at 130 ° C. for 30 minutes was measured by K / S value, and reduction cleaning (80 ° C. using thiourea dioxide 2 g / liter, caustic soda 2 g / liter) The color developability of the polyurethane fiber after treatment for 20 minutes was measured by K / S value, and the reduction cleaning durability was determined by the following formula.
[0097]
Reduction cleaning durability (%) = {(K / S value after reduction cleaning) / (K / S value before reduction cleaning)} × 100
The dye concentration of the metal complex dye is preferably less than 6% omf. Since a measure against blindness is performed by dyeing a metal complex salt dye on polyurethane fiber, even if a dye concentration of 6% omf or more is used, an effect corresponding to the amount of dye used is not obtained, which is uneconomical.
[0098]
In the present invention, the method of dyeing with a disperse dye and a metal complex dye includes a one-bath one-step dyeing method in which the disperse dye and the metal complex dye are used in the same bath, or the above-mentioned mixed product with the metal complex dye first. Then, a two-bath method of dyeing with a disperse dye is mentioned.
[0099]
The dyeing conditions in the case of dyeing by the one bath method are the dyeing conditions with disperse dyes that are usually applied to polyester fibers and the like. That is, as a dyeing bath, dyeing is performed for 20 to 40 minutes at a temperature of 100 to 135 ° C. using a dye solution containing a dispersion leveling agent, a pH adjusting agent and the like in addition to the dye.
[0100]
When the metal complex dye is dyed first by the two-bath method, the dyeing conditions usually applied to polyamide fibers, wool, etc. may be applied.
[0101]
In the present invention, regardless of which dyeing method is employed, it is important to carry out reduction washing in an alkaline bath after dyeing with a disperse dye in order to obtain a mixed dyed product having excellent fastness performance.
[0102]
The reducing cleaning conditions in the alkaline bath may be those normally applied to polyester fibers. For example, caustic soda and soda ash are used as the alkaline component, and hydrosulfite, thiourea dioxide, Rongalite are used as the reducing agent. C (sodium sulfoxylate formaldehyde), Rongalit CL, Rongalit Z, etc. may be used. At this time, the concentration of the alkali component and the concentration of the reducing agent are each preferably 1 to 10 g / liter.
[0103]
Further, a carrier generally used as a fiber swelling agent, for example, chlorobenzene, methylnaphthalene, orthophenylphenol, aromatic ether, aromatic ester or the like may be used in combination of 0.5 to 5 g / liter. It doesn't matter. In addition, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl amine, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl amine ether, polyoxyethylene alkyl benzyl ammonium chloride, alkyl having affinity for polyurethane fiber Picolium chloride or the like may be used in an amount of 0.5 to 5 g / liter. The temperature of the reduction cleaning is not particularly limited, but is preferably in the range of 40 to 90 ° C., and the treatment time is preferably 10 to 40 minutes.
[0104]
In the mixed dyed product dyed with the disperse dye and the metal complex dye as described above, the disperse dye in the polyurethane fiber is removed by reduction washing in an alkaline bath after dyeing with the disperse dye. Since it is combined with a tertiary nitrogen compound, the amount of dropout is relatively small, and there is no change in hue, and the color of the polyurethane fiber retains the same color as the disperse dyeable fiber. As described above, according to the present invention, it is possible to obtain a mixed dyed product of a disperse dyeable dyeable fiber and a polyurethane fiber, which has high color developability, has no eye-opening, and is excellent in dyeing fastness.
[0105]
In the present invention, more preferably, when dyeing with a disperse dye, the dye is treated with a polyvalent metal compound and tannic acid and then dyed (treatment method before dyeing), or when dyeing, the polyvalent metal compound and tannin. By using acid together (combined dyeing method), disperse dyes can be remarkably suppressed from dyeing on polyurethane fibers and can be selectively dyed on disperse dyeable fibers. A mixed dyed product of disperse dye-dyeable fiber and polyurethane fiber having a certain degree is obtained.
[0106]
By such a method, disperse dyes on polyurethane fibers can be remarkably reduced in all disperse dyes regardless of the structure type of disperse dyes, so that disperse dyes in polyurethane fibers can be removed during alkali reduction cleaning. It is easy to carry out, and it is possible to solve the fastness problem related to the problem of contamination of disperse dyes on polyurethane fibers at once.
[0107]
However, when a polyester ether elastic fiber is used as the polyurethane fiber, even if dyeing is performed in a dyeing bath containing tannic acid and a polyvalent metal compound at the time of dyeing, an effect of suppressing dispersion contamination to the polyester ether elastic fiber is not recognized. .
[0108]
Here, as the polyvalent metal compound, an antimony compound is preferable, but as others, tin, aluminum, zinc, barium, bismuth compound can be used, and these polyvalent metal compounds may be used in combination.
[0109]
As the antimony compound, an antimony tartrate salt is preferable, and antimony sodium tartrate and antimony potassium tartrate are exemplified, and antimony sodium tartrate is particularly preferably applicable.
[0110]
The amount of the polyvalent metal compound used is preferably 0.01 to 1.5% omf, more preferably 0.02 to 0.5% omf. Within this range, the effect of the use of the polyvalent metal compound is exhibited, the object of the present invention is sufficiently achieved, and the cost is economical.
[0111]
As the tannic acid, tannin obtained from pentaploid or gallic is preferred, and the amount used is preferably 0.1 to 10% omf, more preferably 0.2 to 5% omf in terms of product concentration. Within this range, the effects of the use of tannic acid are exhibited, the object of the present invention is sufficiently achieved, and the cost is economical.
[0112]
The ratio of the amount of polyvalent metal compound and tannic acid used is preferably 1: 1 to 1:40, more preferably 1: 3 to 1:20, and still more preferably 1: 3 to 1:10. is there.
[0113]
The treatment method before dyeing described above is preferably a method in which the mixed article used in the present invention is immersed in an aqueous solution containing a polyvalent metal compound and tannic acid, and the treatment temperature is preferably 40 to 130 ° C, and 60 to 100 ° C. The treatment time is preferably 10 to 40 minutes. At this time, the pH of the treatment solution is preferably adjusted to 3 to 5 with a pH adjusting agent such as acetic acid.
[0114]
As described above, the premixed mixed article may be dyed with a disperse dye and a metal complex dye.
[0115]
The combined dyeing method in which the polyvalent metal compound and the tannic acid coexist in the dye bath of the disperse dye may use the dyeing conditions normally applied to the polyester fiber, and dissolve the polyvalent metal compound and tannic acid in the dye aqueous solution. And dyeing at a temperature of 100 to 135 ° C. for 20 to 40 minutes. At this time, the pH of the aqueous dye solution is preferably adjusted to 4 to 5 with a pH adjusting agent such as acetic acid.
[0116]
As the dispersion leveling agent used in this case, it is preferable to use alkylnaphthalene-based polyalkylene oxide adducts such as β-naphthalenesulfonic acid formaldehyde condensates and polyalkylene oxide adducts and sulfates thereof.
[0117]
In the present invention, the alkaline reduction washing conditions after dyeing with the disperse dye are such that the amount of the disperse dye attached to the polyurethane fiber is small. Therefore, the reducing agent concentration and the alkaline agent concentration in the reduction washing are 2 to 4 g / liter, respectively. The conditions are sufficient, the processing temperature does not need to be increased, and the reduction cleaning conditions do not need to be strengthened. There is almost no.
[0118]
Treatment with a dye bath in which tannic acid and a polyvalent metal compound coexist in the dye bath of the disperse dye suppresses the dye from being dispersed on the polyurethane fiber and promotes the distribution of the disperse dye to the disperse dyeable fiber This is a treatment that focuses on the action of the disperse dye, and not only the disperse dyes on the polyurethane fiber are remarkably suppressed, but also the disperse dye that diffuses into the polyurethane fiber is quickly decomposed by alkali reduction washing after dyeing, Almost completely removed. As a result, the wet dyeing fastness of the mixed dyed product is remarkably increased, and a mixed dyed product in which the contamination of the dry cleaning liquid is significantly reduced is obtained. In addition, according to the present invention, the disperse dyes can be dyed on the dispersible dyeable fiber, the waste of the dyes can be reduced, and it is possible to prepare a mixed dyed product with high color development and good appearance. In addition, there is an effect of suppressing color variation for each dyeing batch and improving the operation rate of the dyeing machine.
[0119]
In the combined dyeing method in which the polyvalent metal compound and tannic acid coexist in the same bath dyeing bath of the disperse dye and the metal complex dye, the effect of suppressing the dyeing of the disperse dye onto the polyurethane fiber is not changed. Moreover, the effect of suppressing dyeing is exhibited in any disperse dye regardless of the structural type of the disperse dye.
[0120]
Further, since the tertiary nitrogen compound is contained in the polyurethane fiber, there is almost no adverse effect on the dyeing of the metal complex dye on the polyurethane fiber. Therefore, the mixed dyed product after alkaline reduction washing has disperse dyes on disperse dye-dyeable fibers and metal complex dyes on polyurethane fibers. This is an excellent quality mixed dyeing product.
[0121]
In the case where the mixed article of disperse dyeable fiber and polyurethane fiber used in the present invention is a fabric, it is preferable that after knitting and weaving, relaxed and scoured before dyeing. Scouring is preferably performed at a temperature of 60 to 98 ° C. with the fabric as relaxed as possible for reasons such as improving the stretch recovery of the fabric. In addition, what is necessary is just to preset by dry heat at the temperature of 170-200 degreeC when you want to fix form before dyeing | staining. Next, after the reduction cleaning, finishing may be performed according to a conventional method. However, when the final set temperature is lower by 10 ° C. or more than the preset temperature and set at 170 ° C. or less, preferable results are obtained.
[0122]
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further, this invention is not limited at all by these Examples.
[0123]
“Part” represents “wt part”, and measurement methods, evaluation methods, and the like are as follows.
[0124]
(1) Washing fastness
The mixed dyed product was evaluated according to JIS L-0844 A-2 method.
[0125]
The degree of contamination of the test piece and the attached white cloth piece was judged by comparing with the gray scale for color change and the gray scale for contamination, respectively.
[0126]
In addition, for liquid contamination after washing, 8 cc of the contaminated liquid after the test was taken in a porcelain container (20 mm × 40 mm × 10 mm), and the degree of color fading was determined by comparing the degree of liquid contamination with a gray scale for contamination.
[0127]
Good ones with little color fading were rated as grade 5, and those with large color fading were judged as grade 1 in order.
[0128]
(2) Fastness to sweat alkali
The mixed dyed product was evaluated using an alkaline artificial sweat in accordance with JIS L-0848-A method.
[0129]
The degree of contamination of the test piece and the attached white cloth piece was judged by comparing with the gray scale for color change and the gray scale for contamination, respectively.
[0130]
(3) Contamination of dry cleaning liquid
A dry cleaning test was performed on the mixed dyed product in accordance with JIS L-0860.
[0131]
8 cc of the dry cleaning liquid and the dirty liquid after the dry cleaning test were taken in a porcelain container (20 mm × 40 mm × 10 mm), and the degree of color fading was determined by comparing the degree of liquid contamination with a gray scale for contamination.
[0132]
Good ones with little color fading were rated as grade 5, and those with large color fading were judged as grade 1 in order.
[0133]
(4) Color development (L value)
The L value in the Lab color system was measured on the surface of the mixed dyed product (fabric) using a spectrocolorimeter (manufactured by Kollmorgen, model Macbeth MS-2020). The lower the L value, the higher the color developability.
[0134]
(5) Eye opening
The color of the polyurethane fiber visible when the mixed dyed product (fabric) was pulled was determined. When the color of the disperse dyeable fiber is almost the same as that of the disperse dyeable fiber, the color of the polyurethane fiber is extremely different from the color of the disperse dyeable fiber, such as reddish or yellowish. X (open eye state) was determined.
[0135]
(6) Method of measuring ηsp / c
ηsp / c was determined by dissolving the polymer in a solvent of o-chlorophenol at 90 ° C. at a concentration of 1 g / deciliter, then transferring the resulting solution to an Ostwald viscosity tube at 35 ° C., and calculating by the following formula: .
[0136]
ηsp / c = (T / T ₀ ) / C
Where T is the sample solution drop time (seconds), T ₀ Represents the solvent fall time (seconds), and C represents the solution concentration (g / deciliter).
[0137]
(7) Fineness (decitex) of polyurethane fiber and polyester ether elastic fiber
Under an atmosphere of 20 ° C. and a relative humidity of 65%, the polyurethane fiber or the polyester ether elastic fiber is placed in a straight line with no tension and no charge, and is allowed to shrink. Thereafter, 10 samples cut at a length of 1000 mm are weighed together and converted into mass (g) per 10000 m, and the value is defined as fineness (decitex).
[0138]
[Example 1]
ηsp / c = 0.65, TiO ₂ Polyethylene terephthalate having a content of 0.4% was spun at a spinning temperature of 290 ° C., and wound at a winding speed of 7200 m / min by a spin take-up method to obtain a 56 dtex / 24 f yarn. This yarn corresponds to an easily dyeable polyester fiber (dye exhaustion rate = 91%).
[0139]
1000 parts of polytetramethylene ether glycol having a number average molecular weight of 1700 and 235.6 parts of 4,4′7-diphenylmethane diisocyanate are reacted in a nitrogen gas stream at 85 ° C. for 2 hours with stirring, and isocyanate groups are bonded to both ends. An intermediate polymer was obtained. Next, after cooling to room temperature, 1853 parts of dry dimethylformamide was added and dissolved therein. Separately, 19.94 parts of ethylenediamine and 3.1 parts of diethylamine were dissolved in 1922 parts of dry dimethylformamide, and when the above-mentioned intermediate polymer solution was added thereto at room temperature, the mixed solution reacted promptly to increase the viscosity. A polyurethane solution of 2200 poise (30 ° C.) was obtained.
[0140]
Next, 100 g N, N-bis (2-hydroxypropyl) -1,1-dimethylpropylamine and 79.3 g N-butyl-bis (2-hydroxyethyl) amine and 198.7 g isophorone diisocyanate and 378 g To a N, N-dimethylacetamide solution of 0.15 g of dibutyltin dilaurate as a catalyst while stirring at room temperature in dry nitrogen gas, the mixture was stirred for 1 hour, and then the system was brought to 70 ° C. and further reacted for 5 hours. 2270 cm of unreacted isocyanate groups in the reaction solution in the infrared spectrum. ^-1 The reaction was terminated after confirming the disappearance of absorption. The solubility parameter δ of the obtained copolymer polyurethane compound was 10.86.
[0141]
3 parts of the obtained copolymer polyurethane compound and 2 parts of titanium oxide containing a small amount of bluing agent were added to the polyurethane solution, and then uniformly dispersed and dissolved. This solution was defoamed and 311 dtex polyether-based polyurethane fibers were obtained by ordinary dry spinning. The obtained polyurethane fiber was excellent in the properties of high elongation.
[0142]
A 6-course / satin net knitted fabric (course density: 170 loops / 2.54 cm, well density: 40 loops / 2.54 cm) was produced using the above-described readily dyeable polyester fibers and polyurethane fibers under normal knitting conditions. (The mixing ratio of polyurethane fibers is 23 wt%).
[0143]
Next, after scouring and relaxing at 90 ° C. in an expanded form, it was pre-set at 190 ° C. and dyed under the following conditions.
[0144]
(Dyeing conditions)
Disperse dye: Dynics Navy UN-SE (200) (Dystar Japan Co., Ltd.): 3.5% omf
Metal complex dye; Lanacin Navy-S-DNL (disulfonate dye, reduction cleaning durability 71.9%, manufactured by Clariant Japan KK): 2% omf
Dispersing leveling agent; Nikka Sun Salt RM-340 (manufactured by Nikka Chemical Co., Ltd.): 0.5 g / liter
Acetic acid; 0.5cc / liter
Sodium acetate; 1 g / liter
Bath ratio; 1:20
Dyeing temperature, time: 120 ° C, 30 minutes
After completion of the dyeing, the dyeing residual liquid was discharged from the dyeing machine, water was added to the dyeing machine, the temperature was raised to 75 ° C., the following chemicals were added thereto, and the following concentration was adjusted.
[0145]
Thiourea dioxide; 2 g / liter
Caustic soda; 2 g / liter
Sun Mall RC-700 (non-ionic detergent; manufactured by Nikka Chemical Co., Ltd.); 0.5 g / liter
Bath ratio; 1:30
With this reducing cleaning solution, the dyed product is subjected to reducing cleaning at 75 ° C. for 15 minutes, the remaining solution is discharged, the dyeing product is sufficiently rinsed with hot water and water, and then set at 160 ° C. for 30 seconds by dry heat. Finished with.
[0146]
The dyed product thus obtained was evaluated for fastness to washing, fastness to sweat alkali, and dry cleaning liquid contamination. The results are shown in Table 1.
[0147]
In addition, the polyether-based polyurethane fiber of the obtained dyed product had an amber color almost the same as the readily dyeable polyester fiber.
[0148]
[Example 2]
The same procedure as in Example 1 was used, except that the same knitted fabric as in Example 1 was used and dyed in combination with the following concentrations of tannic acid and sodium antimony tartrate in the dyeing bath of the disperse dye and the metal complex dye. Staining was performed.
[0149]
Tannic acid: 2.0% omf
Antimony sodium tartrate: 0.2% omf
After dyeing, reduction washing was performed and finished in the same manner as in Example 1.
[0150]
The dyed product thus obtained was evaluated for fastness to washing, fastness to sweat alkali, contamination with dry cleaning solution, and eye opening. The results are shown in Table 1.
[0151]
In addition, the polyether-based polyurethane fiber of the obtained dyed product had an amber color almost the same as the readily dyeable polyester fiber.
[0152]
[Comparative Example 1]
In Example 1, a dyeing process was performed and finished in the same manner as in Example 1 except that the dye was dyed only with the disperse dye without using the metal complex dye. The results are shown in Table 1.
[0153]
From the above results, the dyed product according to the dyeing method of the present invention has high color developability, no puncture, and the wash fastness is extremely good at 4th grade or more, and there is little dry cleaning liquid contamination (3rd grade or more). It is clear that a product with high commercial value was obtained.
[0154]
On the other hand, the dyed product according to Comparative Example 1 has good fastness performance, but has low color developability, the polyether-based polyurethane fiber is reddish, has a dullness, and has a low commercial value. It has been found.
[0155]
Example 3
The polyurethane solution obtained in Example 1 was mixed with 1.5 wt% of an isobutylene adduct of a polyaddition product of p-cresol and dicyclopentadiene and 2.5 wt% of N, N-bis (2-hydroxyethyl) -t-butylamine. 2- (2′-hydroxy-3 ′, 5-dibenzyl-phenyl) -benzotriazole 0.3 wt%, magnesium stearate 0.05 wt%, and N- (2-aminoethyl) piperazine, 4,4-diphenylmethane After adding 6 wt% of a urea compound having an average number of urea bond units consisting of diisocyanate and phenyl isocyanate (molar ratio 2: 1: 2) and 3 wt% of the copolymer polyurethane compound obtained in Example 1 , Uniformly dispersed and dissolved. This solution was degassed to obtain a 33 dtex polyether polyurethane fiber by ordinary dry spinning.
[0156]
Next, polyethylene terephthalate 84dtex / 36f (manufactured by Kuraray Co., Ltd., SN-2000) and the 33 dtex polyurethane fiber obtained above were twisted and twisted 2.5 times at 800 T / m in the S direction. Were used for warps (warp density 140 / 2.54 cm) and wefts (weft density 100 / 2.54 cm), respectively, to prepare 2/1 twill fabrics (polyurethane fiber mixing ratio 9%).
[0157]
The obtained mixed fabric was scoured and relaxed by a conventional method, then pre-set at 200 ° C., and dyed under the following conditions.
[0158]
(Dyeing conditions)
Disperse dye: Dispersol Black XF (manufactured by Mitsui BASF Dye Co., Ltd., diester type disperse dye): 14% omf
Metal complex dye; Eisen Opal Black New (monosulfonate dye, reduction cleaning durability 62.6%, manufactured by Hodogaya Chemical Co., Ltd.): 1% omf
Dispersing leveling agent; Nikka Sun Salt RM-340 (manufactured by Nikka Chemical Co., Ltd.): 0.5 g / liter
Acetic acid; 0.5 cc / liter
Sodium acetate; 1 g / liter
Bath ratio; 1:20
Dyeing temperature, time: 130 ° C, 30 minutes
After completion of the dyeing, the dyeing residual liquid was discharged from the dyeing machine, water was added to the dyeing machine, the temperature was raised to 80 ° C., the following chemicals were added thereto, and the following concentration was adjusted.
[0159]
Thiourea dioxide; 4 g / liter
Caustic soda; 4 g / liter
Sun Mall RC-700 (non-ionic detergent; manufactured by Nikka Chemical Co., Ltd.); 0.5 g / liter
Bath ratio; 1:30
With this reducing cleaning solution, the dyed product is subjected to reducing cleaning at 80 ° C. for 20 minutes, the remaining solution is discharged, and the dyed product is sufficiently rinsed with hot water and water, and then set at 170 ° C. for 30 seconds with a dry heat set. Finished.
[0160]
The dyed product thus obtained was evaluated for fastness to washing, fastness to sweat alkali, and dry cleaning liquid contamination. The results are shown in Table 1.
[0161]
In addition, the polyether-based polyurethane fiber of the obtained dyed product had a black hue almost equivalent to the easily dyeable polyester fiber.
[0162]
Example 4
The same as in Example 3, except that a pre-set fabric similar to that in Example 3 was used and dyed in combination with the following concentrations of tannic acid and sodium antimony tartrate in a dyeing bath of a disperse dye and a metal complex dye. Staining was performed.
[0163]
Tannic acid: 1.0% omf
Antimony sodium tartrate: 0.25% omf
After completion of the dyeing, the dyeing residual liquid was discharged from the dyeing machine, water was added to the dyeing machine, the temperature was raised to 80 ° C., the following chemicals were added thereto, and the following concentration was adjusted.
[0164]
Thiourea dioxide; 2 g / liter
Caustic soda; 2 g / liter
Sun Mall RC-700 (non-ionic detergent; manufactured by Nikka Chemical Co., Ltd.); 0.5 g / liter
Bath ratio; 1:30
With this reducing cleaning solution, the dyed product is subjected to reducing cleaning at 80 ° C. for 20 minutes, the remaining liquid is discharged, the dyed product is sufficiently rinsed with hot water and water, and then set at 170 ° C. for 30 seconds by dry heat. Finished with.
[0165]
The dyed product thus obtained was evaluated for fastness to washing, fastness to sweat alkali, contamination with dry cleaning solution, and eye opening. The results are shown in Table 1.
[0166]
In addition, the polyether-based polyurethane fiber of the obtained dyed product had a black hue almost equivalent to the easily dyeable polyester fiber.
[0167]
[Comparative Example 2]
In Example 3, dyeing was performed and finished in the same manner as in Example 3 except that the dye was dyed only with the disperse dye without using the metal complex dye. The results are shown in Table 1.
[0168]
From the above results, the dyed product according to the dyeing method of the present invention has high color developability, no puncture, and the wash fastness is extremely good at 4th grade or more, and there is little dry cleaning liquid contamination (3rd grade or more). It is clear that a product with high commercial value was obtained.
[0169]
On the other hand, the dyed product according to Comparative Example 2 has good fastness performance, but has low color developability, the polyether-based polyurethane fibers are reddish, crisp, and have a low commercial value. It was.
[0170]
[Table 1]

[0171]
【The invention's effect】
According to the present invention, a disperse dyeable dyeable fiber and a polyurethane fiber, which have not been obtained so far, have high color developability, no puncture, excellent fastness to washing, and extremely little dry cleaning liquid contamination. A mixed dyeing product is obtained.

Claims (3)

Disperse dyeable fiber and polyurethane fiber are mixed products, polyurethane fiber contains tertiary nitrogen compound, disperse dyeable fiber is dyed with disperse dye, polyurethane fiber is metal A mixed dyed product of a disperse dyeable dyeable fiber and a polyurethane fiber, which is dyed with a complex salt dye.   The disperse dye according to claim 1, wherein the fastness to washing in the JIS L-0844 A-2 method is 3 to 4 or higher and the contamination of the dry cleaning liquid in the JIS L-0860 method is 3 or higher. Mixed dyed product of dyeable fiber and polyurethane fiber. Disperse dyeable fiber and polyurethane fiber containing tertiary nitrogen compound are dyed with disperse dye and metal complex dye by one-bath method or two-bath method. After dyeing with disperse dye, alkali reduction A method for producing a mixed dyed product of disperse dyeable dyeable fibers and polyurethane fibers, which comprises washing.