JP3592779B2

JP3592779B2 - Reactive dye composition and dyeing method using the same

Info

Publication number: JP3592779B2
Application number: JP03017695A
Authority: JP
Inventors: 利夫檜原; 陽介高橋
Original assignee: ダイスタージャパン株式会社
Priority date: 1994-04-07
Filing date: 1995-01-27
Publication date: 2004-11-24
Anticipated expiration: 2019-11-24
Also published as: JPH08104822A

Description

【０００１】
【産業上の利用分野】
本発明は赤色反応染料と青色反応染料からなる紫色系反応染料組成物及び更にこれに黄色反応染料を配合してなるブラウン系反応染料組成物に関する。
更に赤色、青色及び黄色各成分の染着速度が揃った反応染料組成物及びそれを用いる染色法に関する。
【０００２】
【従来の技術】
反応染料は色相が鮮明で、豊富であり、しかも諸堅牢度に優れているので、広く使用されている。しかし反応染料は、反応基の種類により染色速度が異なっている。更にその構造によってもその染色速度が異なっている。例えば遊離酸の形で下記一般式〔Ｉ−Ａ〕
【０００３】
【化１４】

【０００４】
（式中、Ｒ^０、Ｒ^１及びＲ^２は水素原子又はＣ_１〜Ｃ_３のアルキル基を表わし、Ｒ^３は水素原子、ハロゲン原子又はＣ_１〜Ｃ_３アルキル基を表わし、Ｘは−ＣＨ＝ＣＨ_２基、−Ｃ_２Ｈ_４ＯＳＯ_３Ｈ基又は−Ｃ_２Ｈ_４Ｃｌ基を表わす。）
にて示されるビニルスルホン系の赤色反応染料は吸尽染色法において無機塩の依存性が小さく、耐光性、塩素堅牢度に優れている。又下記一般式〔Ｉ−Ｂ〕
【０００５】
【化１５】

【０００６】
〔式中ＬはＯＨ基又はＸを表わし（ここでＸは前記と同様の意義を有する）、Ｍは
【０００７】
【化１６】

【０００８】
を表わし（ここでＲ^１は前記と同様の意義を有し、Ｗは水素原子、カルボキシル基、スルホン酸基、Ｃ_１〜Ｃ_３アルキル基又はＳＯ_２Ｘ（Ｘは前記と同様の意義を有する）を表わす）、ｍは０又は１を表わす。〕
にて示されるビニルスルホン系の赤色反応染料も吸尽染色法において無機塩の依存性が小さく、塩素堅牢度、ビルドアップ性に優れている。従ってこの優れた特性を生かして巾広い色相の染色に赤色原色として活用する要求は多い。
【０００９】
【発明が解決しようとする課題】
しかし、この赤色染料を使って紫色相を得るように青色染料と配合して染色をした場合、染色速度の違いから、染色時間の経過に伴なって色相が変化し、色調の再現性が得にくい。具体的には、例えば遊離酸の形で、下記一般式〔ＩＩ〕
【００１０】
【化１７】

【００１１】
（式中、Ｘ及びＬは前記と同様の意義を有する。）
で示される青色反応染料、遊離酸の形で下記一般式〔ＩＩＩ〕
【００１２】
【化１８】

【００１３】
で示される青色反応染料、遊離酸の形で下記一般式〔ＩＶ〕
【００１４】
【化１９】

【００１５】
（式中、Ｒ^５は水素原子又はＣ_１〜Ｃ_３アルコキシ基を表わし、Ｒ^６は水素原子、Ｃ_１〜Ｃ_３アルキル基又はＣ_１〜Ｃ_３アルコキシ基を表わし、Ｘは前記と同様の意義を有する。）
で示される青色反応染料及び遊離酸の形で下記一般式〔Ｖ〕
【００１６】
【化２０】

【００１７】
（式中、Ｘは前記と同様の意義を有する。）
で示される青色反応染料は無機塩の依存性が小さく、特に前記一般式〔ＩＩ〕、〔ＩＩＩ〕及び〔Ｖ〕で示される反応染料は塩素堅牢度に優れているが、前記一般式〔Ｉ−Ａ〕又は〔Ｉ−Ｂ〕で示される赤色染料に比べ染着速度が速く、とりわけ一般式〔ＩＩＩ〕で示される染料が著しく速い。その結果、一般式〔Ｉ−Ａ〕又は〔Ｉ−Ｂ〕で示される赤色反応染料とこれら一般式〔ＩＩ〕、〔ＩＩＩ〕、〔ＩＶ〕及び〔Ｖ〕で示される青色反応染料との配合により得られる紫色系反応染料組成物を用いて染色を施した場合、染色時間の経過に伴って、染布が青味から赤味へと変化していく。このことは、染色の再現性を得る上で不利である。
【００１８】
それ故、前記一般式〔Ｉ−Ａ〕及び／又は〔Ｉ−Ｂ〕で示される赤色反応染料と染色速度の揃った青色反応染料の開発が要望される。このことは紫色染色に限らず、ブラウン染色においても、青色反応染料と共に黄色反応染料について同じく染色速度の揃ったものの選択や、開発が要望される。
【００１９】
【課題を解決するための手段】
本発明者等はかかる要求を満たすよう、種々検討した結果、本発明に到達した。
即ち、本発明は遊離酸の形で前記一般式〔Ｉ−Ａ〕及び／又は〔Ｉ−Ｂ〕で示される水溶性反応染料を赤色成分として用い、これに青色成分として、遊離酸の形で前記一般式〔ＩＩ〕、〔ＩＩＩ〕、〔ＩＶ〕及び〔Ｖ〕で示される反応染料からなる群から選ばれた少くとも１種の反応染料９０〜３０重量％と遊離酸の形で下記一般式〔ＶＩ−Ａ〕及び／又は〔ＶＩ−Ｂ〕で示される反応染料１０〜７０重量％からなる青色反応染料混合物を配合してなる紫色系反応染料組成物及びこれを用いるセルロース繊維の染色法を要旨とするものである。
一般式〔ＶＩ−Ａ〕
【００２０】
【化２１】

【００２１】
（式中、Ｒ^７は水素原子又はＣ_１〜Ｃ_３アルキル基を表わし、Ａはフェニレン基、Ｃ_２〜Ｃ_３アルキレン基又はＣ_２〜Ｃ_３アルキレンオキシＣ_２〜Ｃ_３アルキレン基を表わし、Ｚは塩素原子、フッ素原子、水酸基、シアノアミノ基、スルホエチルアミノ基又はスルホフェニルアミノ基を表わし、Ｘは前記と同様の意義を有する。）
一般式〔ＶＩ−Ｂ〕
【００２２】
【化２２】

【００２３】
（式中、Ｒ^７、Ａ、Ｚ及びＸは前記と同様の意義を有する。）
又、本発明は前記紫色系反応染料組成物及び黄色成分として遊離酸の形で下記一般式〔ＶＩＩ〕で示される反応染料６０〜４０重量％と遊離酸の形で下記一般式〔ＶＩＩＩ〕で示される反応染料４０〜６０重量％からなる黄色反応染料混合物を配合してなるブラウン系反応染料組成物、並びに前記紫色系反応染料組成物及び黄色成分として遊離酸の形で下記一般式〔ＶＩＩ〕で示される反応染料８０〜６０重量％と遊離酸の形で下記一般式〔ＩＸ〕で示される反応染料２０〜４０重量％からなる黄色反応染料混合物を配合してなるブラウン系反応染料組成物を要旨とするものである。
一般式〔ＶＩＩ〕
【００２４】
【化２３】

【００２５】
（式中、Ｘは前記と同様の意義を有する。）
一般式〔ＶＩＩＩ〕
【００２６】
【化２４】

【００２７】
（式中、Ｔはアミノ基又はメチル基を表わし、Ｘは前記と同様の意義を有する。）
一般式〔ＩＸ〕
【００２８】
【化２５】

【００２９】
（式中、Ｘは前記と同様の意義を有する。）
又、本発明は前記紫色系反応染料組成物及び黄色成分として遊離酸の形で前記一般式〔ＶＩＩ〕で示される反応染料６０〜４０重量％と遊離酸の形で前記一般式〔ＶＩＩＩ〕で示される反応染料４０〜６０重量％からなる黄色反応染料混合物１００重量部に遊離酸の形で下記一般式〔Ｘ〕で示される反応染料５〜３０重量部混合してなる黄色反応染料混合物を配合してなるブラウン系反応染料組成物を要旨とするものである。
一般式〔Ｘ〕
【００３０】
【化２６】

【００３１】
（式中、Ｘは前記と同様の意義を有する。）
又、本発明は、前記紫色系反応染料組成物及び黄色成分として遊離酸の形で前記一般式〔ＶＩＩ〕で示される反応染料８０〜６０重量％と遊離酸の形で前記一般式〔ＩＸ〕で示される反応染料２０〜４０重量％からなる黄色反応染料混合物１００重量部に遊離酸の形で前記一般式〔Ｘ〕で示される反応染料５〜３０重量部混合してなる黄色反応染料混合物を配合してなるブラウン系反応染料組成物を要旨とするものである。
【００３２】
更に、本発明はこれらのブラウン系反応染料組成物を用いるセルロース繊維の染色法を要旨とするものである。
以下、詳細に本発明を説明する。
前記一般式〔Ｉ−Ａ〕、〔Ｉ−Ｂ〕、〔ＩＶ〕、〔ＶＩ−Ａ〕及び〔ＶＩ−Ｂ〕においてＲ^０、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^６、Ｒ^７及びＷで表わされるＣ_１〜Ｃ_３のアルキル基としてはメチル基、エチル基、ｎ−プロピル基及びｉｓｏ−プロピル基が挙げられる。特にメチル基、エチル基が好ましい。
【００３３】
前記一般式〔ＩＩＩ〕及び〔ＩＶ〕において、Ｒ^４，Ｒ^５およびＲ^６で表わされるＣ_１〜Ｃ_３のアルコキシ基としてはメトキシ基、エトキシ基、ｎ−プロポキシ基、ｉｓｏ−プロポキシ基が挙げられる。特にメトキシ基及びエトキシ基が好ましい。Ｒ^３で表わされるハロゲン原子としては臭素原子及び塩素原子が挙げられる。
【００３４】
前記一般式〔ＶＩ−Ａ〕及び〔ＶＩ−Ｂ〕におけるＡで表わされるＣ_２〜Ｃ_３アルキレン基及びＣ_２〜Ｃ_３アルキレンオキシＣ_２〜Ｃ_３アルキレン基としてはエチレン基、プロピレン基、エチレンオキシエチレン基及びプロピレンオキシプロピレン基が挙げられる。
−Ａ−ＳＯ_２Ｘ基の具体例としては、β−（β−スルファトエチルスルホニル）エチル基、β−（β−クロロエチルスルホニル）エチル基、γ−（β−クロロエチルスルホニル）プロピル基、γ−（β−スルファートエチルスルホニル）プロピル基、β−（ビニルスルホニル）エチル基、β−〔β−（β−スルファトエチルスルホニル）エトキシ〕エチル基、β−〔β−（β−クロロエチルスルホニル）エトキシ〕エチル基、γ−〔γ−（β−スルファートエチルスルホニル）プロポキシ〕プロピル基、β−〔β−（ビニルスルホニル）エトキシ〕エチル基等が挙げられる。
【００３５】
特にβ−（β−スルファトエチルスルホニル）エチル基、（−Ｃ_２Ｈ_４ＳＯ_２Ｃ_２Ｈ_４ＯＳＯ_３Ｈ）、γ−（β−スルファトエチルスルホニル）プロピル基、（−Ｃ_３Ｈ_６ＳＯ_２Ｃ_２Ｈ_４ＯＳＯ_３Ｈ）、β−〔β−（β−スルファトエチルスルホニル）エトキシ〕エチル基（−Ｃ_２Ｈ_４ＯＣ_２Ｈ_４ＳＯ_２Ｃ_２Ｈ_４ＯＳＯ_３Ｈ）等が好ましいものとして例示される。
前記一般式〔Ｉ−Ａ〕〜〔Ｘ〕で示される化合物は公知であり、公知の合成方法で合成することができる。
【００３６】
本発明の染料組成物における、青色及び黄色の各反応染料の混合割合は以下の通りである。
即ち、一般式〔ＩＩ〕、〔ＩＩＩ〕、〔ＩＶ〕及び〔Ｖ〕で示される反応染料からなる群から選ばれる少くとも一種の反応染料と一般式〔ＶＩ−Ａ〕及び／又は〔ＶＩ−Ｂ〕で示される反応染料からなる青色反応染料混合物における混合割合は、前者を９０〜３０重量％と後者を１０〜７０重量％の範囲から選ばれる。特に好ましくは前者を７０〜４０重量％と後者を３０〜６０重量％の割合である。
【００３７】
更に、特に好ましくは前者７０〜４０重量％のうち５０〜４０重量％が下記構造式〔ＩＶ′〕
【００３８】
【化２７】

【００３９】
で示される反応染料である混合物である。
なお、一般式〔ＶＩ−Ａ〕及び〔ＶＩ−Ｂ〕で示される反応染料において、Ｚがフッ素原子の場合にＡがフェニレン基であると染着速度が速過ぎて好ましくない。
【００４０】
又、一般式〔ＶＩＩ〕で示される反応染料と一般式〔ＶＩＩＩ〕で示される反応染料からなる黄色反応染料混合物の混合割合は前者が６０〜４０重量％と後者が４０〜６０重量％であり、一般式〔ＶＩＩ〕で示される反応染料と一般式〔ＩＸ〕で示される反応染料からなる黄色反応染料混合物の場合は前者が８０〜６０重量％と後者が２０〜４０重量％である。
又、一般式〔ＶＩＩ〕で示される反応染料と一般式〔ＶＩＩＩ〕で示される反応染料混合物或は一般式〔ＶＩＩ〕で示される反応染料と一般式〔ＩＸ〕で示される反応染料混合物に更に一般式〔Ｘ〕で示される反応染料を配合する場合には前者１００重量部に対し後者を５〜３０重量部の割合で配合する。三者のそれぞれの混合割合は、一般式〔ＶＩＩ〕で示される反応染料を５５〜４５重量％、一般式〔ＶＩＩＩ〕で示される反応染料３５〜２５重量％及び一般式〔Ｘ〕で示される反応染料２０〜１０重量％並びに一般式〔ＶＩＩ〕で示される反応染料６０〜４０重量％、一般式〔ＩＸ〕で示される反応染料３０〜２０重量％及び一般式〔Ｘ〕で示される反応染料２０〜１０重量％の中から選定するのが好ましい。
【００４１】
これら上述の組成物を用いることにより、吸尽染色法のみならず連続染色法、コールドパッドバッチ法においても染色速度が合致しておりその用途は非常に大きい。
赤色反応染料に配合される青色反応染料混合物の場合は、赤色反応染料１００重量部に対し青色反応染料混合物はいずれも５〜５０００重量部、好ましくは１０〜１０００重量部である。
【００４２】
紫色系反応染料組成物に配合される黄色反応染料混合物はいずれも赤色反応染料１００重量部に対して５〜５０００重量部、好ましくは１０〜１０００重量部である。
本発明の染料組成物において、色合せ及び耐光堅牢度を更に向上させるために更に他の赤色系、黄色系或は青色系の反応染料を配合する場合には１０重量％までの範囲ならば、その特性に影響は殆んどなく、差支えない。この青色系反応染料としてはＣ．Ｉ．ＲｅａｃｔｉｖｅＢｌｕｅ１９が例示される。
【００４３】
本発明の染料組成物を構成する各反応染料は、いずれも遊離酸又はその塩の形で存在するが、通常、その塩としては、リチウム塩、ナトリウム塩、カリウム塩及びカルシウム塩などのアルカリ金属塩又はアルカリ土類金属塩が好ましい。
本発明の染色法の対象となるセルロース繊維としては、木綿、ビスコースレーヨン及びキュプラアンモニウムレーヨン、麻等を挙げることができる。これらのセルロース繊維はポリエステル、トリアセテート、ジアセテート、ポリアクリロニトリル、ポリアミド、羊毛及び絹等の繊維との混合繊維の形をとっていてもよい。
【００４４】
本発明の二原色又は三原色の水溶性反応染料組成物を用いる染色法によりセルロース繊維を吸尽染色するには、重炭酸ソーダ、炭酸ソーダ、炭酸リチウム、苛性ソーダ、トリエチルアミン等のアルカリ及び芒硝、食塩等の無機塩の存在下に染色する。この際のアルカリの使用量は、通常染色浴１リットル当り１０〜３０ｇである。また無機塩の使用量は染色浴１リットル当り３０〜５０ｇ程度が適当である。
【００４５】
染色温度は４０℃〜８０℃、好ましくは５０℃〜６０℃である。染色後の染色物は、ソーピング及び水洗処理した後乾燥する。
本発明による反応染料組成物は、更にコールドパッドバッチ法等の連続染色法にも適用可能であることはいうまでもない。
【００４６】
【実施例】
次に、実施例を上げて本発明を具体的に説明するが、本発明は、これらの実施例に限定されるものではない。
実施例１
赤色成分として、下記構造式〔Ｉ−Ａ−１〕
【００４７】
【化２８】

【００４８】
で示される反応染料０．０５ｇ、青色成分として、下記構造式〔ＩＩＩ −１〕
【００４９】
【化２９】

【００５０】
で示される反応染料０．０２ｇ及び下記構造式〔ＶＩ−Ａ−１〕
【００５１】
【化３０】

【００５２】
で示される反応染料０．０２ｇよりなる反応染料組成物を、３０℃の水１７０ｍｌに溶解し、これに芒硝１０ｇ添加して染色用ポットを調製し、これに木綿布１０ｇを挿入し、振盪式染色機にて２５分間振盪させ、その後ソーダ灰水溶液（１００ｇ／ｌ）を３０ｍｌ添加し、５分間、同温度で振盪後１℃／分の割合で６０℃まで３０分間かけて昇温した。
【００５３】
上述の染色用ポットを６個調製し、染色温度が３５℃、４０℃、５０℃、６０℃、６０℃×１０分及び６０℃×６０分それぞれに達した時間で各染色ポットから染色布を取出し、これを水洗し、酢酸２ｇ／ｌの水溶液にて中和し、水洗し、８０℃で１０分間湯洗後、ヘキストジャパン製ＨｏｓｔａｐａｌＣＴ−４０（登録商標）２ｇ／ｌのソーピング浴にて１００℃×１０分間ソーピングし、水洗、乾燥し、それぞれ▲１▼、▲２▼、▲３▼、▲４▼、▲５▼及び▲６▼とした。
▲１▼から▲６▼までの染色布は一定の染色で均染性よく次第に濃くなっており赤色染料と青色染料の染色速度がよく一致していた。
【００５４】
比較例１
赤色成分として前記構造式〔Ｉ−Ａ−１〕で表わされる反応染料０．０５ｇ及び青色成分として遊離酸の形で前記構造式〔ＩＩＩ −１〕で示される反応染料０．０５ｇを用い、実施例１に準じて染色を実施した。
▲６▼の６０℃×６０分の染色布を基準とし、▲１▼〜▲５▼の染色布と対比した。その結果染色温度が比較的低い温度、即ち▲５▼より▲１▼に行くに従って青味が強くなり、これは赤色染料と青色染料の染色速度が一致していないことを表わし、また、染色再現性が得にくいことを示している。
【００５５】
実施例２〜４
実施例１において赤色染料及び青色染料を表−１に記載の混合割合に変えた以外すべて実施例１と同様に操作した。その結果、染色布は表−１記載の一定の色相に均染性よく濃くなっており赤色反応染料と青色反応染料の染着速度がよく一致していることを示していた。
【００５６】
【表１】

【００５７】
実施例５〜１９
実施例１において青色成分として表−２−Ａ及び表−２−Ｂに記載の構造式で示される染料を用いた以外はすべて実施例１と同様に操作した。
その結果染色布は一定の暗紫色で次第に濃くなっており、赤色反応染料と青色反応染料の染着速度がよく一致していることを示していた。
【００５８】
【表２】

【００５９】
【表３】

【００６０】
【表４】

【００６１】
【表５】

【００６２】
【表６】

【００６３】
【表７】

【００６４】
【表８】

【００６５】
【表９】

【００６６】
【表１０】

【００６７】
【表１１】

【００６８】
【表１２】

【００６９】
実施例２０−１〜２０−２４
実施例１において赤色染料として表−３−Ａの２０−１〜２０−４に記載の染料を用い、又実施例５において赤色染料として表−３−Ａの２０−５〜２０−８に記載の染料を用い、更に実施例６において赤色染料として表−３−Ａの２０−９〜２０−１４に記載の染料を用いた以外は、それぞれ実施例１，５，６に準じて同様の操作を施した。
【００７０】
次に、実施例１において赤色染料として表−３−Ｂの２０−１５及び２０−１６に記載の染料を用い、又実施例において赤色染料として表−３−Ｂの２０−１７及び２０−１８に記載の染料を用い、更に実施例６において赤色染料として表−３−Ｂの２０−１９〜２０−２４に記載の染料を用いた以外は、それぞれ実施例１，５，６に準じて同様の操作を施した。
その結果、染色布は一定の暗紫色で次第に濃くなっており、赤色染料と青色染料の染着速度はよく一致していた。
【００７１】
【表１３】

【００７２】
【表１４】

【００７３】
【表１５】

【００７４】
【表１６】

【００７５】
【表１７】

【００７６】
【表１８】

【００７７】
実施例２１−１〜２１−１０
実施例１において青色染料として表−４の２１−１〜２１−３に記載の染料を用い、又実施例５において青色染料として表−４の２１−４〜２１−６に記載の染料を用い、更に実施例６において青色染料として表−４の２１−７〜２１−１０に記載の染料を用いた以外は、それぞれ実施例１，５，６に準じて同様の操作を施した。
その結果、染色布は一定の暗紫色で次第に濃くなっており赤色染料と青色染料の染着速度はよく一致していた。
【００７８】
【表１９】

【００７９】
【表２０】

【００８０】
実施例２２−１〜２２−６
下記構造式で示される黄色反応染料を表−５に示す割合で混合した６種類の黄色反応染料混合物をそれぞれ実施例１、５、６、１４、１６及び２０−２１の赤色反応染料と青色反応染料に加えて実施例１に準じて同様の操作を施した。その結果、得られた染色布はそれぞれ一定のブラウン色で次第に濃くなって、赤色染料と青色染料及び黄色染料の染着速度がよく一致していることを示した。
【００８１】
【化３１】

【００８２】
【化３２】

【００８３】
【化３３】

【００８４】
【化３４】

【００８５】
【化３５】

【００８６】
【化３６】

【００８７】
【表２１】

【００８８】
実施例２３−１〜２３−６
実施例１、５、６、１４、１６及び２０−１６において色相調整の為、染色速度がほぼ一致している下記構造染料で表わされる青色染料０．００４ｇを配合して実施例１に準じて同様の操作をした。その結果、染色布は一定のやや鮮明な紫色で次第に濃くなっていた。
【００８９】
【化３７】

【００９０】
実施例２４
実施例１において赤色染料として下記の式で示される染料を混合比１：１で混合した染料混合物を用い、実施例１に準じて同様の操作を施した。その結果、染色布は一定の暗紫色で次第に濃くなっており、赤色染料と青色染料の染着速度はよく一致していた。
【００９１】
【化３８】

【００９２】
実施例２５
実施例１で使用した構造式〔Ｉ−Ａ−１〕、〔ＩＩＩ −１〕及び〔ＶＩ−Ａ−１〕で示される反応染料並びに実施例２２−１で使用した構造式〔ＶＩＩ −１〕及び〔ＩＸ−１〕で示される反応染料を用いて、下記組成のパディング液を調製した。
〔Ｉ−Ａ−１〕４．０ｇ
〔ＩＩＩ −１〕０．８ｇ〔ＶＩ−Ａ−１〕１．０ｇ
〔ＶＩＩ −１〕１．０ｇ〔ＩＸ−１〕１．５ｇ
アルギン酸ナトリウム（中粘度品）２．０ｇ
ｍ−ニトロベンゼンスルホン酸ナトリウム１０．０ｇ
ヘキサメタリン酸ソーダ２．０ｇ
界面活性剤２ｍｌ
（ＬｏｎｉｌＳＲ−Ｊヘキストジャパン社製）
【００９３】
このパディング液に木綿布を含浸し、絞り率７０％に搾液し、１００℃で３分間乾燥した。次に、芒硝２００ｇ／ｌ、炭酸ナトリウム４０ｇ／ｌ及び３８°Ｂｅ水酸化ナトリウム水溶液１５ｍｌ／ｌを含有するケミカル液を含浸させ、絞り率８０％に搾液し、１０２℃で３０秒、６０秒、１２０秒間スチーミング固着し、水洗後、酢酸２ｇ／ｌの水溶液にて中和、水洗、湯洗後ヘキストジャパン社製ＨｏｓｔａｐａｌＣＴ−４０（登録商標）２ｇ／ｌのソーピング浴にて１００℃で１０分間ソーピングし、水洗し、乾燥した。その結果、染色布は一定色相のブラウンで次第に濃くなっており、赤色染料、黄色染料及び青色染料の染色速度がよく一致していることを示していた。
【００９４】
【発明の効果】
本発明は特定の赤色反応染料にこの染料と染着速度が一致した青色反応染料を配合してなる良好な均染性を備えた紫色系反応染料組成物及び更にこれに黄色反応染料を配合してなる三者の染着速度が一致した均染性の良好なブラウン系反応染料組成物を提供するものであり、セルロース繊維を紫色からブラウン色に均一に再現性よく染色することを容易にするものである。[0001]
[Industrial applications]
The present invention relates to a violet reactive dye composition comprising a red reactive dye and a blue reactive dye, and further relates to a brown reactive dye composition comprising a yellow reactive dye added thereto.
Further, the present invention relates to a reactive dye composition having a uniform dyeing rate for each of red, blue and yellow components, and a dyeing method using the same.
[0002]
[Prior art]
Reactive dyes are widely used because they have clear hues, are rich, and have excellent fastnesses. However, the dyeing speed of the reactive dye varies depending on the type of the reactive group. Furthermore, the dyeing speed differs depending on the structure. For example, in the form of a free acid, the following general formula [IA]
[0003]
Embedded image

[0004]
(Wherein, R ⁰ , R ¹ and R ² represent a hydrogen atom or a C ₁ -C ₃ alkyl group, R ³ represents a hydrogen atom, a halogen atom or a C ₁ -C ₃ alkyl group, and X represents —CH = CH ₂ group _represents a -C ₂ H 4 OSO ₃ H group or _-C 2 _H 4 Cl group.)
The vinyl sulfone-based red reactive dye represented by the formula (1) has little dependence on inorganic salts in the exhaust dyeing method, and is excellent in light resistance and chlorine fastness. Also, the following general formula [IB]
[0005]
Embedded image

[0006]
Wherein L represents an OH group or X (where X has the same meaning as described above), and M represents
Embedded image

[0008]
(Where R ¹ has the same meaning as described above, W is a hydrogen atom, a carboxyl group, a sulfonic acid group, a C ₁ -C ₃ alkyl group or SO ₂ X (X has the same meaning as described above) )), And m represents 0 or 1. ]
The vinyl sulfone-based red reactive dye represented by the formula (1) also has a small dependence on inorganic salts in the exhaust dyeing method, and is excellent in chlorine fastness and build-up properties. Therefore, there are many demands for utilizing these excellent characteristics as a red primary color for dyeing a wide range of hues.
[0009]
[Problems to be solved by the invention]
However, when using this red dye and dyeing it with a blue dye so as to obtain a purple hue, the hue changes over time due to the difference in dyeing speed, and color tone reproducibility is obtained. Hateful. Specifically, for example, in the form of a free acid, the following general formula [II]
[0010]
Embedded image

[0011]
(In the formula, X and L have the same meaning as described above.)
In the form of a blue reactive dye or free acid represented by the following general formula [III]:
[0012]
Embedded image

[0013]
In the form of a blue reactive dye or free acid represented by the following general formula [IV]
[0014]
Embedded image

[0015]
(Wherein, R ⁵ represents a hydrogen atom or a C ₁ -C ₃ alkoxy group, R ⁶ represents a hydrogen atom, a C ₁ -C ₃ alkyl group or a C ₁ -C ₃ alkoxy group, and X represents the same as the above. It has significance.)
In the form of a blue reactive dye and a free acid represented by the following general formula [V]
[0016]
Embedded image

[0017]
(In the formula, X has the same meaning as described above.)
The blue reactive dye represented by the formula (1) has a small dependence on inorganic salts. In particular, the reactive dyes represented by the formulas (II), (III) and (V) have excellent chlorine fastness, but the formula (I) The dyeing speed is higher than that of the red dye represented by -A] or [IB], and the dye represented by the general formula [III] is particularly fast. As a result, a blend of a red reactive dye represented by the general formula [IA] or [IB] and a blue reactive dye represented by the general formulas [II], [III], [IV] and [V] When dyeing is performed using the purple reactive dye composition obtained by the above, the dyed fabric changes from blue to red with the elapse of the dyeing time. This is disadvantageous in obtaining reproducibility of staining.
[0018]
Therefore, development of a red reactive dye represented by the general formulas [IA] and / or [IB] and a blue reactive dye having a uniform dyeing speed is desired. This is not limited to purple dyeing, but also for brown dyeing, selection and development of yellow reactive dyes having the same dyeing speed as blue reactive dyes are required.
[0019]
[Means for Solving the Problems]
The present inventors have conducted various studies to satisfy such demands, and as a result, have reached the present invention.
That is, the present invention uses the water-soluble reactive dye represented by the above general formula [IA] and / or [IB] in the form of a free acid as a red component, and uses the water-soluble reactive dye as a blue component in the form of a free acid. 90 to 30% by weight of at least one reactive dye selected from the group consisting of the reactive dyes represented by the general formulas [II], [III], [IV] and [V] and a free acid in the form of A purple reactive dye composition containing a blue reactive dye mixture comprising 10 to 70% by weight of a reactive dye represented by the formulas [VI-A] and / or [VI-B], and a method for dyeing cellulose fibers using the same. It is the gist.
General formula [VI-A]
[0020]
Embedded image

[0021]
(Wherein, R ⁷ represents a hydrogen atom or a C ₁ -C ₃ alkyl group, A represents a phenylene group, a C ₂ -C ₃ alkylene group or a C ₂ -C ₃ alkyleneoxy C ₂ -C ₃ alkylene group, Z represents a chlorine atom, a fluorine atom, a hydroxyl group, a cyanoamino group, a sulfoethylamino group or a sulfophenylamino group, and X has the same meaning as described above.)
General formula [VI-B]
[0022]
Embedded image

[0023]
(In the formula, R ⁷ , A, Z and X have the same meaning as described above.)
The present invention also relates to a violet reactive dye composition and 60 to 40% by weight of a reactive dye represented by the following general formula [VII] in the form of a free acid as a yellow component, and a free acid in the form of the following general formula [VIII]. A brown reactive dye composition prepared by mixing a yellow reactive dye mixture comprising 40 to 60% by weight of the reactive dye shown above, and the violet reactive dye composition and a free acid as a yellow component represented by the following general formula [VII]: A brown reactive dye composition comprising 80 to 60% by weight of a reactive dye represented by the following formula and 20 to 40% by weight of a reactive dye represented by the following general formula [IX] in the form of a free acid: It is a summary.
General formula [VII]
[0024]
Embedded image

[0025]
(In the formula, X has the same meaning as described above.)
General formula [VIII]
[0026]
Embedded image

[0027]
(In the formula, T represents an amino group or a methyl group, and X has the same meaning as described above.)
General formula [IX]
[0028]
Embedded image

[0029]
(In the formula, X has the same meaning as described above.)
Also, the present invention relates to the violet reactive dye composition and 60 to 40% by weight of the reactive dye represented by the general formula [VII] in the form of a free acid as a yellow component and the general formula [VIII] in the form of a free acid. A yellow reactive dye mixture obtained by mixing 5 to 30 parts by weight of a reactive dye represented by the following general formula [X] in the form of a free acid with 100 parts by weight of a yellow reactive dye mixture consisting of 40 to 60% by weight of the reactive dye shown below. The present invention provides a brown reactive dye composition comprising:
General formula [X]
[0030]
Embedded image

[0031]
(In the formula, X has the same meaning as described above.)
The present invention also relates to the violet reactive dye composition and 80 to 60% by weight of the reactive dye represented by the general formula [VII] in the form of a free acid as the yellow component and the general formula [IX] in the form of a free acid. A yellow reactive dye mixture obtained by mixing 5 to 30 parts by weight of a reactive dye represented by the above general formula [X] with 100 parts by weight of a yellow reactive dye mixture comprising 20 to 40% by weight of a reactive dye represented by the formula The gist is a brown reactive dye composition to be blended.
[0032]
The present invention further provides a method for dyeing cellulose fibers using the brown reactive dye composition.
Hereinafter, the present invention will be described in detail.
In the general formulas [IA], [IB], [IV], [VI-A] and [VI-B], R ⁰ , R ¹ , R ² , R ³ , R ⁶ , R ⁷ and W the alkyl group of _C 1 -C ₃ represented in a methyl group, an ethyl group, and n- propyl, and iso- propyl group. Particularly, a methyl group and an ethyl group are preferable.
[0033]
In the general formulas [III] and [IV], the C ₁ -C ₃ alkoxy groups represented by R ⁴ , R ⁵ and R ⁶ include a methoxy group, an ethoxy group, an n-propoxy group and an iso-propoxy group. Can be Particularly, a methoxy group and an ethoxy group are preferred. The halogen atom represented by R ³ includes a bromine atom and a chlorine atom.
[0034]
Examples of the C ₂ -C ₃ alkylene group and C ₂ -C ₃ alkyleneoxy C ₂ -C ₃ alkylene group represented by A in the general formulas [VI-A] and [VI-B] include an ethylene group, a propylene group, and an ethylene group. Oxyethylene groups and propyleneoxypropylene groups are mentioned.
Specific examples of the -A-SO ₂ X group include a β- (β-sulfatoethylsulfonyl) ethyl group, a β- (β-chloroethylsulfonyl) ethyl group, a γ- (β-chloroethylsulfonyl) propyl group, γ- (β-sulfatoethylsulfonyl) propyl group, β- (vinylsulfonyl) ethyl group, β- [β- (β-sulfatoethylsulfonyl) ethoxy] ethyl group, β- [β- (β-chloroethyl Sulfonyl) ethoxy] ethyl group, γ- [γ- (β-sulfatoethylsulfonyl) propoxy] propyl group, β- [β- (vinylsulfonyl) ethoxy] ethyl group and the like.
[0035]
In particular, β- (β-sulfatoethylsulfonyl) ethyl group, (—C ₂ H ₄ SO ₂ C ₂ H ₄ OSO ₃ H), γ- (β-sulfatoethylsulfonyl) propyl group, (—C ₃ H ₆ SO ₂ C ₂ H ₄ OSO ₃ H), β- [β- (β-sulfatoethylsulfonyl) ethoxy] ethyl group (—C ₂ H ₄ OC ₂ H ₄ SO ₂ C ₂ H ₄ OSO ₃ H) and the like. It is exemplified as preferred.
The compounds represented by the general formulas [IA] to [X] are known and can be synthesized by a known synthesis method.
[0036]
The mixing ratio of each of the blue and yellow reactive dyes in the dye composition of the present invention is as follows.
That is, at least one reactive dye selected from the group consisting of the reactive dyes represented by the general formulas [II], [III], [IV] and [V] and the general formulas [VI-A] and / or [VI- The mixing ratio in the blue reactive dye mixture comprising the reactive dye represented by B] is selected from the range of 90 to 30% by weight for the former and 10 to 70% by weight for the latter. Particularly preferably, the ratio of the former is 70 to 40% by weight and the latter is 30 to 60% by weight.
[0037]
More preferably, 50 to 40% by weight of the former 70 to 40% by weight has the following structural formula [IV ']
[0038]
Embedded image

[0039]
Is a mixture which is a reactive dye represented by
In addition, in the reactive dyes represented by the general formulas [VI-A] and [VI-B], when Z is a fluorine atom and A is a phenylene group, the dyeing speed is too high, which is not preferable.
[0040]
The mixing ratio of the yellow reactive dye mixture comprising the reactive dye represented by the general formula [VII] and the reactive dye represented by the general formula [VIII] is 60 to 40% by weight for the former and 40 to 60% by weight for the latter. In the case of a yellow reactive dye mixture comprising a reactive dye represented by the general formula [VII] and a reactive dye represented by the general formula [IX], the former is 80 to 60% by weight and the latter is 20 to 40% by weight.
Further, the reactive dye represented by the general formula [VII] and the reactive dye represented by the general formula [VIII] or the reactive dye represented by the general formula [VII] and the reactive dye represented by the general formula [IX] are further added. When the reactive dye represented by the general formula [X] is blended, the latter is blended in an amount of 5 to 30 parts by weight with respect to 100 parts by weight of the former. The mixing ratio of each of the three is represented by 55 to 45% by weight of the reactive dye represented by the general formula [VII], 35 to 25% by weight of the reactive dye represented by the general formula [VIII], and by the general formula [X]. 20 to 10% by weight of a reactive dye, 60 to 40% by weight of a reactive dye represented by the general formula [VII], 30 to 20% by weight of a reactive dye represented by the general formula [IX], and a reactive dye represented by the general formula [X] It is preferable to select from 20 to 10% by weight.
[0041]
By using these compositions, not only the exhaustion dyeing method, but also the continuous dyeing method and the cold pad batch method, the dyeing speeds match, and the use thereof is very large.
In the case of a blue reactive dye mixture to be mixed with a red reactive dye, the amount of the blue reactive dye mixture is 5 to 5,000 parts by weight, preferably 10 to 1,000 parts by weight, based on 100 parts by weight of the red reactive dye.
[0042]
The amount of the yellow reactive dye mixture blended in the violet reactive dye composition is 5 to 5,000 parts by weight, preferably 10 to 1,000 parts by weight, per 100 parts by weight of the red reactive dye.
In the dye composition of the present invention, if further red, yellow or blue reactive dyes are blended to further improve color matching and light fastness, the content is up to 10% by weight. It has little or no effect on its properties. Examples of the blue reactive dye include C.I. I. Reactive Blue 19 is exemplified.
[0043]
Each reactive dye constituting the dye composition of the present invention is present in the form of a free acid or a salt thereof, and the salt is usually an alkali metal such as a lithium salt, a sodium salt, a potassium salt and a calcium salt. Salts or alkaline earth metal salts are preferred.
Examples of the cellulose fibers to be subjected to the dyeing method of the present invention include cotton, viscose rayon, cupra ammonium rayon, hemp and the like. These cellulose fibers may be in the form of fibers mixed with fibers such as polyester, triacetate, diacetate, polyacrylonitrile, polyamide, wool and silk.
[0044]
In order to exhaustively dye cellulose fibers by a dyeing method using the water-soluble reactive dye composition of the two primary colors or three primary colors of the present invention, alkali such as sodium bicarbonate, sodium carbonate, lithium carbonate, caustic soda, triethylamine and inorganic such as sodium sulfate, sodium chloride and the like are used. Stain in the presence of salt. The amount of alkali used at this time is usually 10 to 30 g per liter of the dyeing bath. The amount of the inorganic salt used is suitably about 30 to 50 g per liter of the dyeing bath.
[0045]
The dyeing temperature is from 40C to 80C, preferably from 50C to 60C. The dyed material after dyeing is subjected to soaping and water washing and then dried.
It goes without saying that the reactive dye composition according to the present invention is further applicable to a continuous dyeing method such as a cold pad batch method.
[0046]
【Example】
Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
Example 1
As a red component, the following structural formula [IA-1]
[0047]
Embedded image

[0048]
As a blue component, 0.05 g of a reactive dye represented by the following structural formula [III-1]
[0049]
Embedded image

[0050]
And 0.02 g of the reactive dye represented by the following structural formula [VI-A-1]
[0051]
Embedded image

[0052]
Is dissolved in 170 ml of water at 30 ° C., and 10 g of mirabilite is added thereto to prepare a pot for dyeing, 10 g of cotton cloth is inserted into the pot, and the mixture is shaken. The mixture was shaken with a dyeing machine for 25 minutes, then 30 ml of an aqueous solution of soda ash (100 g / l) was added, and the mixture was shaken at the same temperature for 5 minutes and then heated to 60 ° C. at a rate of 1 ° C./min for 30 minutes.
[0053]
Six dyeing pots were prepared as described above, and the dyed cloth was dyed from each dyeing pot at the time when the dyeing temperature reached 35 ° C, 40 ° C, 50 ° C, 60 ° C, 60 ° C x 10 minutes, and 60 ° C x 60 minutes, respectively. It is taken out, washed with water, neutralized with an aqueous solution of acetic acid 2 g / l, washed with water, washed with hot water at 80 ° C. for 10 minutes, and then washed with a Hostast CT-40 (registered trademark) 2 g / l soap bath. It was soaped at 100 ° C. for 10 minutes, washed with water and dried to obtain (1), (2), (3), (4), (5) and (6), respectively.
The dyed cloths from (1) to (6) were gradually dyed at a constant dyeing level with good levelness, and the dyeing speeds of the red dye and the blue dye were in good agreement.
[0054]
Comparative Example 1
Using 0.05 g of the reactive dye represented by the structural formula [IA-1] as a red component and 0.05 g of the reactive dye represented by the structural formula [III-1] in the form of a free acid as a blue component, Dyeing was carried out according to Example 1.
The dyed cloth of (1) to (5) was compared with the dyed cloth of (6) at 60 ° C. for 60 minutes. As a result, the bluish color becomes stronger as the dyeing temperature goes to a relatively low temperature, that is, from (5) to (1), indicating that the dyeing speeds of the red dye and the blue dye do not match. This indicates that it is difficult to obtain the property.
[0055]
Examples 2 to 4
All operations were performed in the same manner as in Example 1 except that the mixing ratio of the red dye and the blue dye was changed as shown in Table 1. As a result, the dyed cloth had a uniform hue and a uniform hue shown in Table 1, indicating that the dyeing speeds of the red reactive dye and the blue reactive dye were in good agreement.
[0056]
[Table 1]

[0057]
Examples 5 to 19
All operations were performed in the same manner as in Example 1 except that the dyes represented by the structural formulas shown in Tables 2-A and 2-B were used as the blue component.
As a result, the dyed cloth was dark dark purple and gradually became darker, indicating that the dyeing speeds of the red reactive dye and the blue reactive dye were in good agreement.
[0058]
[Table 2]

[0059]
[Table 3]

[0060]
[Table 4]

[0061]
[Table 5]

[0062]
[Table 6]

[0063]
[Table 7]

[0064]
[Table 8]

[0065]
[Table 9]

[0066]
[Table 10]

[0067]
[Table 11]

[0068]
[Table 12]

[0069]
Examples 20-1 to 20-24
In Example 1, the dyes described in 20-1 to 20-4 of Table 3-A were used as red dyes, and in Example 5, the dyes described in 20-5 to 20-8 of Table 3-A were used as red dyes. In the same manner as in Examples 1, 5, and 6, except that the dyes described in Examples 6 to 9 were used as the red dyes in Example 6, and the dyes described in 20-9 to 20-14 of Table 3-A were used. Was given.
[0070]
Next, in Example 1, the dyes described in 20-15 and 20-16 of Table 3-B were used as red dyes, and in Examples, 20-17 and 20-18 of Table 3-B were used as red dyes. In the same manner as in Examples 1, 5, and 6, except that the dye described in Example 1 was used, and the dyes described in Examples 20 to 20 to 24 in Table 3-B were used as red dyes in Example 6. Operation was performed.
As a result, the dyed cloth was dark dark purple and gradually darkened, and the dyeing rates of the red dye and the blue dye were in good agreement.
[0071]
[Table 13]

[0072]
[Table 14]

[0073]
[Table 15]

[0074]
[Table 16]

[0075]
[Table 17]

[0076]
[Table 18]

[0077]
Examples 21-1 to 21-10
In Example 1, the dyes described in Tables 21-1 to 21-3 are used as blue dyes, and in Example 5, the dyes described in 21-4 to 21-6 of Table 4 are used as blue dyes. Further, the same operation as in Examples 1, 5, and 6 was performed, except that the dyes described in 21-7 to 21-10 of Table 4 were used as blue dyes in Example 6.
As a result, the dyed cloth had a certain dark purple color and gradually became darker, and the dyeing rates of the red dye and the blue dye were in good agreement.
[0078]
[Table 19]

[0079]
[Table 20]

[0080]
Examples 22-1 to 22-6
The six types of yellow reactive dye mixtures obtained by mixing the yellow reactive dyes represented by the following structural formulas at the ratios shown in Table 5 were used to react the red reactive dyes and blue reactive dyes of Examples 1, 5, 6, 14, 16 and 20-21, respectively. The same operation as in Example 1 was performed in addition to the dye. As a result, the obtained dyed cloths gradually became darker with a constant brown color, indicating that the dyeing speeds of the red dye, the blue dye and the yellow dye were in good agreement.
[0081]
Embedded image

[0082]
Embedded image

[0083]
Embedded image

[0084]
Embedded image

[0085]
Embedded image

[0086]
Embedded image

[0087]
[Table 21]

[0088]
Examples 23-1 to 23-6
In Examples 1, 5, 6, 14, 16 and 20-16, 0.004 g of a blue dye represented by the following structural dye having almost the same dyeing speed was blended for hue adjustment, according to Example 1. The same operation was performed. As a result, the dyed cloth had a certain bright violet color and gradually became darker.
[0089]
Embedded image

[0090]
Example 24
The same operation as in Example 1 was performed using a dye mixture in which a dye represented by the following formula was mixed at a mixing ratio of 1: 1 as the red dye in Example 1. As a result, the dyed cloth was dark dark purple and gradually darkened, and the dyeing rates of the red dye and the blue dye were in good agreement.
[0091]
Embedded image

[0092]
Example 25
The reactive dyes represented by the structural formulas [IA-1], [III-1] and [VI-A-1] used in Example 1 and the structural formula [VII-1] used in Example 22-1 A padding solution having the following composition was prepared using the reactive dye represented by the formula [IX-1] and [IX-1].
[IA-1] 4.0 g
[III-1] 0.8 g [VI-A-1] 1.0 g
[VII-1] 1.0 g [IX-1] 1.5 g
Sodium alginate (medium viscosity product) 2.0g
Sodium m-nitrobenzenesulfonate 10.0 g
Sodium hexametaphosphate 2.0g
Surfactant 2ml
(Lonil SR-J Hoechst Japan)
[0093]
This padding liquid was impregnated with a cotton cloth, squeezed to a squeezing ratio of 70%, and dried at 100 ° C. for 3 minutes. Next, it is impregnated with a chemical solution containing 200 g / l of sodium sulfate, 40 g / l of sodium carbonate and 15 ml / l of a 38 ° Be aqueous sodium hydroxide solution, squeezed to a squeezing ratio of 80%, and kept at 102 ° C. for 30 seconds and 60 seconds. , Steamed and fixed for 120 seconds, washed with water, neutralized with an aqueous solution of acetic acid 2 g / l, washed with water and washed with hot water, and then washed at 100 ° C. in a 2 g / l soap bath of Hostapal CT-40 (registered trademark). It was soaped for 10 minutes, washed with water and dried. As a result, the dyed cloth gradually became darker with a constant hue of brown, indicating that the dyeing speeds of the red dye, the yellow dye, and the blue dye were in good agreement.
[0094]
【The invention's effect】
The present invention relates to a violet reactive dye composition having good leveling properties obtained by blending a specific red reactive dye with a blue reactive dye having the same dyeing speed as this dye, and further blending a yellow reactive dye therewith. The present invention provides a brown-based reactive dye composition having good leveling properties, in which the dyeing speeds of the three are matched, and makes it easy to dye cellulose fibers uniformly from purple to brown with good reproducibility. Things.

Claims

As a red component, a reactive dye represented by the following general formula [IA] and / or [IB] in the form of a free acid; and as a blue component, a reactive acid represented by the following general formula [II], [III], 90 to 30% by weight of at least one reactive dye selected from the group consisting of the reactive dyes represented by [IV] and [V] and a free acid in the form of the following general formulas [VI-A] and / or [VI] -B] A violet reactive dye composition comprising a blue reactive dye mixture comprising 10 to 70% by weight of a reactive dye represented by the formula:
General formula [IA]

(Wherein, R ⁰ , R ¹ and R ² represent a hydrogen atom or a C ₁ -C ₃ alkyl group, R ³ represents a hydrogen atom, a halogen atom or a C ₁ -C ₃ alkyl group, and X represents —CH ＝ Represents a CH ₂ group, a —C ₂ H ₄ OSO ₃ H group, or a —C ₂ H ₄ Cl group.)
General formula [IB]

Wherein L represents an OH group or X (where X has the same meaning as described above), and M is

(Where R ¹ has the same meaning as described above, W is a hydrogen atom, a carboxyl group, a sulfonic acid group, a C ₁ -C ₃ alkyl group or SO ₂ X (X has the same meaning as described above) )), And m represents 0 or 1. ]
General formula [II]

(In the formula, X and L have the same meaning as described above.)
General formula [III]

General formula [IV]

(Wherein, R ⁵ represents a hydrogen atom or a C ₁ -C ₃ alkoxy group, R ⁶ represents a hydrogen atom, a C ₁ -C ₃ alkyl group or a C ₁ -C ₃ alkoxy group, and X represents the same as the above. It has significance.)
General formula [V]

(In the formula, X has the same meaning as described above.)
General formula [VI-A]

(Wherein, R ⁷ represents a hydrogen atom or a C ₁ -C ₃ alkyl group, A represents a phenylene group, a C ₂ -C ₃ alkylene group or a C ₂ -C ₃ alkyleneoxy C ₂ -C ₃ alkylene group, Z represents a chlorine atom, a fluorine atom, a hydroxyl group, a cyanoamino group, a sulfoethylamino group or a sulfophenylamino group, and X has the same meaning as described above.)
General formula [VI-B]

(In the formula, R ⁷ , A, Z and X have the same meaning as described above.)

The violet reactive dye composition according to claim 1, wherein 60 to 40% by weight of a reactive dye represented by the following general formula [VII] in the form of a free acid as a yellow component and the following general formula [VIII] in the form of a free acid: A brown reactive dye composition comprising a yellow reactive dye mixture comprising 40 to 60% by weight of the reactive dye.
General formula [VII]

(In the formula, X has the same meaning as described above.)
General formula [VIII]

(In the formula, T represents an amino group or a methyl group, and X has the same meaning as described above.)

The violet reactive dye composition according to claim 1, wherein 80 to 60% by weight of the reactive dye represented by the general formula [VII] in the form of a free acid as a yellow component and the following general formula [IX] in the form of a free acid. A brown reactive dye composition comprising a yellow reactive dye mixture comprising 20 to 40% by weight of the reactive dye.
General formula [IX]

(In the formula, X has the same meaning as described above.)

The violet reactive dye composition according to claim 1, wherein 60 to 40% by weight of a reactive dye represented by the general formula [VII] in the form of a free acid as a yellow component and the general formula [VIII] in the form of a free acid. A yellow reactive dye mixture is prepared by mixing 5 to 30 parts by weight of a reactive dye represented by the following general formula [X] in the form of a free acid with 100 parts by weight of a yellow reactive dye mixture consisting of 40 to 60% by weight of a reactive dye. A brown reactive dye composition comprising:
General formula [X]

(In the formula, X has the same meaning as described above.)

The violet reactive dye composition according to claim 1, wherein 80 to 60% by weight of the reactive dye represented by the general formula [VII] as a free component in the form of a free acid and a free acid in the general formula [IX] as a yellow component. A yellow reactive dye mixture obtained by mixing 5 to 30 parts by weight of a reactive dye represented by the above general formula [X] in the form of a free acid with 100 parts by weight of a yellow reactive dye mixture consisting of 20 to 40% by weight of a reactive dye to be prepared. A brown reactive dye composition comprising:

A method for dyeing cellulose fibers, comprising using the dye composition according to any one of claims 1 to 5.