JP3580564B2 - Cobalt-containing azo compound, its use and production method - Google Patents

Description

【０００６】
（式中、Ｘ、Ｙはそれぞれ独立に水素原子、ニトロ基、クロル原子、メチル基、エチル基、スルファモイル基、メトキシ基又はエトキシ基を示す。Ｒ_１ 、Ｒ_２ 、Ｒ_３ はそれぞれ独立に炭素数１〜４の低級アルキル基を示し、Ｒは水素原子またはメチル基を示す。Ｚは水素原子、ニトロ基、クロル原子、メチル基、エチル基、スルファモイル基、メトキシ基又はエトキシ基を示す。また、Ｍは水素又はカチオン残基を表わす。）
【０００７】
で示されるコバルト含有アゾ化合物、その製造方法及びそれを用いる合成又は天然ポリアミド繊維材料の染色法である。
本発明の特徴は、異ったモノアゾ染料２分子にコバルト１原子が錯結合していることで、価値あるコバルト含有アゾ染料が得られることを観察した事実に基いている。
【０００８】
本発明の一般式（４）で示される価値あるコバルト含有アゾ染料の製造は、例えば、次の方法によって行われる。
一般式（１）
【０００９】
【化８】

【００１０】
（式中、Ｘ、Ｙはそれぞれ独立に水素原子、ニトロ基、クロル原子、メチル基、エチル基、スルファモイル基、メトキシ基又はエトキシ基を示す。Ｒ_１ 、Ｒ_２ はそれぞれ独立に炭素数１〜４の低級アルキル基を示し、Ｒは水素原子またはメチル基を示す。）
で表わされるモノアゾ染料と、一般式（２）又は（３）
【００１１】
【化９】

【００１２】
【化１０】

【００１３】
（上記式中、Ｑ、Ｚはそれぞれ独立に水素原子、ニトロ基、クロル原子、メチル基、エチル基、スルファモイル基、メトキシ基又はエトキシ基を示す。Ｒ_３ は、炭素数１〜４の低級アルキル基を示す。）
で表わされるモノアゾ染料とを、各モノアゾ染料１分子に対してコバルト１原子が錯結合するようにコバルト付与剤を作用させることによって行われる。
【００１４】
一般式（１）で示されるモノアゾ染料は、例えば、３−（ジメチルアミノ）フェノール、３−（ジエチルアミノ）フェノール、３−（ジブチルアミノ）フェノール、３−（ジプロピルアミノ）フェノール、３−（ジエチルアミノ）フェノール、３−（ジメチルアミノ）−４−メチルフェノール、３−（ジエチルアミノ）−４−メチルフェノール、３−（ジブチルアミノ）−４−メチルフェノールと、ジアゾ化された２−アミノ−フェノール、２−アミノ−４−ニトロフェノール、２−アミノ−５−ニトロフェノール、２−アミノ−４−クロルフェノール、２−アミノ−４−メチルフェノール、２−アミノ−４−メトキシフェノール、２−アミノ−４−クロル−６−ニトロ−フェノール、２−アミノ−４−ニトロ−６−クロル−フェノール、２−アミノ−４−メチル−６−ニトロ−フェノールなどとを弱酸性、中性または弱アルカリ性の媒質中でカップリング反応させることによって容易に得られる。
【００１５】
前記一般式（２）又は（３）で示されるモノアゾ染料は、例えば、６−アミノ−Ｎ−メチル−２−ナフタレンスルホンアミド、６−アミノ−Ｎ−エチル−２−ナフタレンスルホンアミド、６−アミノ−Ｎ−プロピル−２−ナフタレンスルホンアミド、６−アミノ−Ｎ−ブチル−２−ナフタレンスルホンアミド、６−ヒドロキシ−Ｎ−メチル−２−ナフタレンスルホンアミド、６−ヒドロキシ−Ｎ−エチル−２−ナフタレンスルホンアミド、６−ヒドロキシ−Ｎ−プロピル−２−ナフタレンスルホンアミド、６−ヒドロキシ−Ｎ−ブチル−２−ナフタレンスルホンアミドと、ジアゾ化された２−アミノ−フェノール、２−アミノ−４−ニトロフェノール、２−アミノ−５−ニトロフェノール、２−アミノ−４−クロルフェノール、２−アミノ−４−メチルフェノール、２−アミノ−４−メトキシフェノール、２−アミノ−４−クロル−６−ニトロ−フェノール、２−アミノ−４−クロル−５−ニトロフェノール、２−アミノ−４−ニトロ−６−クロルフェノール、２−アミノ−４−メチル−６−ニトロ−フェノール２−アミノ−４，６ジニトロフェノールとをカップリング反応させることにより容易に製造することができる。
【００１６】
本発明は、異ったモノアゾ染料２分子にコバルト１原子が錯結合しているいわゆる非対称型コバルト錯塩染料であることを特徴とするが、製造方法によっては、同一のモノアゾ染料２分子にコバルト１原子が錯結合しているいわゆる対称型コバルト錯塩染料、すなわち一般式（１）の１：２コバルト染料、一般式（２）の１：２コバルト染料又は一般式（３）の１：２コバルト染料が生成し、これら対称型コバルト錯塩染料がかなりの比率で含有されてくる場合があるが、かかる混合染料でもポリアミド繊維の染色に好ましい結果をもたらすことがあり、本発明に含まれる。
【００１７】
本発明の目的とする一般式（４）で示されるコバルト含有アゾ化合物の製造の他の方法としては、一般式（１）及び一般式（２）又は（３）で示されるモノアゾ染料合成の各成分（ジアゾ成分、カップリング成分）とコバルト付与剤とを任意の順序で混合し、例えば少なくとも一種のジアゾ成分のジアゾ化物と、少なくとも２種のカップリング成分の混合物とを反応させて得られる少なくとも２種の金属を含まないモノアゾ染料混合物にコバルト付与剤を作用させて、同時的に一般式（４）で示されるモノアゾ化合物を製造する方法が考えられる。この方法は、工程簡略化が可能となり、工業的に有利な製造方法となり得る。
【００１８】
本発明方法において使用するモノアゾ染料は、その合成および沈澱生成の後に乾燥しないで湿ったペーストの形で次の処理に使用するのが有利である。
次に、該モノアゾ染料とコバルト付与剤との反応は公知の方法が適用され、例えばこれらのモノアゾ染料を、水又はメタノール、アセトン、グリコール類等の水性媒質中、モノアゾ染料ベースに対して、０．５１〜０．６モル比のコバルト付与剤を用い、温度７０〜１１０℃、好ましくは９０〜９５℃で行われる。
【００１９】
ここで、コバルト付与剤としては、例えば、硫酸コバルト、酒石酸コバルト、酢酸コバルト等が用いられる。
この際、コバルト化の触媒として、アルカノールアミン等の有機アミン類、苛性ソーダ、ソーダ灰等のアルカリ剤を用いることが出来る。
【００２０】
本発明のモノアゾ染料の製造におけるジアゾ化物及びカップリング成分のモル比は、約１：１に近い程一層よい結果が得られる。好ましい比率は１：１〜１．１である。
本発明の方法によって得られる一般式（４）で示される目的とするコバルト含有アゾ染料の取り出しは、通常の方法によって塩析、濾過、乾燥し、或いは水溶液のまま、スプレイ乾燥し、又は必要により濃縮し、有機溶媒を加え、濃厚水溶液の形で染色に供することもできる。
【００２１】
本発明の方法によって得られるコバルト含有アゾ染料は、非常に多くの種類の物質を染色および捺染するのに適している。特にこの化合物は動物性物質、例えば絹、皮革特に羊毛の染色に適しているが、ポリアミド、ポリウレタン等から作られた合成繊維材料の染色および捺染にも適している。特にポリアミド系合成皮革、スゥエード材料に対してカラーバリューが高く、諸堅牢度のすぐれた鮮明な青色乃至紫色に染色するのに適する。
【００２２】
本発明の方法によって得られるコバルト含有アゾ染料は、弱アルカリ性〜弱酸性の浴から染色することができるが、特に中性または僅かに酸性例えば酢酸若しくは硫安を含んでいる浴から適用して好結果が得られる。こうして得られた染色物は均一であって日光、洗濯等に対して良好な堅牢度を示すが特にその鮮明度およびビルドアップ性において優れている。
【００２３】
【発明の効果】
本発明のコバルト含有アゾ染料は、特に動物性物質、例えば絹、皮革、特に羊毛の染色に適しているが、ポリアミド、ポリウレタンおよびポリアクリロニトリルから作られた合成繊維材料の染色および捺染にも適している。また、ポリアミド系合成皮革、特にスゥエード調の材料に対してカラーバリューが高く、諸堅牢度のすぐれた鮮明な青色乃至紫色に染色する。
【００２４】
【実施例】
以下の実施例によって本発明を具体的に説明する。なお、実施例中、部は重量部を表わす。
【００２５】
実施例１
ジアゾ化反応釜に、１２００部の水、９２．５部の２−アミノ−５−ニトロ−１−ハイドロキシベンゼン、４７重量％の苛性ソーダ５６．５部を攪拌して溶解する。次いで、１００重量％硫酸８７部、氷４８０部を加え、３〜５℃る冷却してから３６重量％亜硝酸ソーダ１１６部を約３０分を要して注入し、５〜１０℃で１時間攪拌して、ジアゾ化を完了させる。
【００２６】
カップリング反応釜に、水１０００部と、２−アミノナフタリン−６−スルホン酸−Ｎ−メチルアミド１４８．６部を仕込み、よく分散させる。氷３２０部を加えて２０℃に冷却し、これを先のジアゾ化反応釜に３０分で注入してから分散剤（ＱＭＣ・４１％品、２００部）を加えて、１０〜２０℃で数時間攪拌する。この間ｐＨを０．５〜１．５に保持するように調整する。
濾過、洗浄して約８００部（乾燥重量２３６部）のモノアゾ染料のウエットケーキ（Ａ）が得られた。
【００２７】
一方、他のジアゾ化反応釜に、１４００部の水と、３６重量％の塩酸１４６部を加え、この中に１０７．８部の２−アミノ−５−ニトロ−１−ハイドロキシベンゼンを加えてよく分散し、氷７００部を加えて３〜５℃に冷却する。これに３６重量％亜硝酸ソーダ１３９部を約３０分を要して注入し、５〜１０℃で１時間攪拌して、ジアゾ化を完了させ、酢酸ソーダ７０部を加えてｐＨ４〜５に調整する。
【００２８】
次に、カップリング反応釜に、水２８００部と、１１７部の１−ハイドロキシ−３−ジエチルアミノベンゼン及び４７重量％苛性ソーダ７１部を仕込み、攪拌溶解し、更に１４０部のソーダ灰及び９００部の氷を加える。
次に、この中に先のジアゾ化液を約３０分で注入し、温度１５〜２０℃で、ｐＨ１０〜１０．５で数時間かけてカップリング反応を完了させる。
塩析、濾過、洗浄して約７００部（乾燥重量２１０部）のモノアゾ染料のウエットケーキ（Ｂ）が得られた。
【００２９】
〔コバルト化〕
反応釜に、水５０００部、前記モノアゾ染料（Ａ）（乾燥重量換算で２１１部）及び４７重量％苛性ソーダ５５部を加え、ｐＨ１２〜１２．５に調整し、加温溶解させる。滓取りろ過を行ない、次いでモノアゾ染料（Ｂ）（乾燥重量換算で１７６部）及びジエタノールアミン５０部を加え、９０〜９５℃に昇温する。
一方、別の反応釜に、１５００部の水と２２５部のソーダ灰を溶解しておく。更に別反応釜に水６００部と１４１部の硫酸コバルト及び８０部の酒石酸を加えて溶解しておき、これら二つの水溶液を前記混合モノアゾ染料中に１時間で並行して注入し、コバルト化を完了させる。
【００３０】
次いで、塩析、濾過、洗浄、乾燥して５８７部の目的とするコバルト含有アゾ染料を得た。この染料はλｍａｘ ５８４ｎｍ（ｐＨ＝７の緩衝液中）であり、水に良く溶解して赤味の鮮明青色を呈する。また、この染料は、本発明の非対称型１：２コバルト染料を主成分とし、他にモノアゾ染料（Ａ）の対称型１：２コバルト染料及びモノアゾ染料（Ｂ）の対称型１：２コバルト染料をそれぞれ約２０重量％を含有する混合染料である。
【００３１】
〔染色例１〕
上記の方法によって得られた染料０．１ｇを水１００ｇに溶解し、ミニカラー染色試験機の染色ポットに入れ、これにスエード調のポリアミド系人工皮革２．０ｇを投入して蓋をした。この染色ポットを内温４０℃のミニカラー染色機に挿入し、９０℃まで５０分間で昇温した。９０℃で３０分間保温したのち、染色ポットを取り出し冷却する。被染物を取り出し、常法に従って洗浄した。かくして得られた染色物は、鮮明なネイビーブルー色を呈し、諸堅牢度も良好であった。
【００３２】
〔染色例２〕
上記の方法によって得られた染料０．１ｇを水３００ｇに溶解し、カラーペット染色機の染色ポットに入れ、これにナイロンスパン糸５．０ｇと硫安０．１５ｇを投入した。４０℃から染色を開始し、１００℃まで６０分間で昇温し、１００℃で１０分間保温した。ついで１０％酢酸０．５ｍｌを加え、更に２０分間保温を続けた。その後、被染物を取り出し、常法に従って洗浄した。かくして得られた染色物は、鮮明なネイビー色を呈し、諸堅牢度も良好であった。
【００３３】
実施例１〜１７
実施例１において用いた一般式（１）のモノアゾ染料として以下の表−１及び表−２に記載されたモノアゾ染料（Ｎｏ． ２〜１７）を用い、実施例１と同様にして、右欄に示す色相の優れた染色性を有するコバルト含有アゾ染料が得られた。なお、表−１には実施例１の染料もＮｏ．１として併記した。
【００３４】
【表−１】

【００３５】
【表−２】

【００３６】
実施例１８
ジアゾ化反応釜に、１２００部の水、９２．５部の２−アミノ−５−ニトロ−１−ハイドロキシベンゼン、４７重量％の苛性ソーダ５６．５部を攪拌して溶解する。次いで、１００重量％硫酸８７部、氷４８０部を加え、３〜５℃る冷却してから３６重量％亜硝酸ソーダ１１６部を約３０分を要して注入し、５〜１０℃で１時間攪拌して、ジアゾ化を完了させる。
【００３７】
カップリング反応釜に、水１５００部と、２−ヒドロキシナフタリン−６−スルホン酸−Ｎ−メチルアミド１４９．２部、４７重量％の苛性ソーダ１２７．４部及びソーダ灰６４部を攪拌溶解し、更に氷８００部で０〜５℃に冷却しておく。これに先のジアゾ化反応液を約３０分で注入する。液温５〜１０℃、ｐＨは１２〜１２．５になる。
【００３８】
この後、３５重量％塩酸５０部を水２５部で希釈した塩酸水を加え、ｐＨ１１〜１１．５にして１０〜１５時間攪拌し、次に３５重量％塩酸３０部を水１５部に希釈した塩酸水でｐＨ９．５〜１０に調整する。液量約６５００部となる。
カップリング反応の終点を確認（レゾルシンのアンモニア水溶液で発色なしを確認）後、７０℃に昇温し、工業塩６５０部を加えて塩析後、濾過、洗浄して湿ケーキ約１０００部（乾燥重量１９２部）のモノアゾ染料のウエットケーキ（Ｃ）が得られた。収率約８０％。
【００３９】
〔コバルト化〕
反応釜に、水５０００部、実施例１で得られたモノアゾ染料（Ｂ）（乾燥重量換算で１７６部）及び前記の方法で得られたモノアゾ染料（Ｃ）（乾燥重量換算で１９２部）及び４７重量％苛性ソーダ８５部及びソーダ灰１０６部を加え、７５〜８０℃に昇温する。液量約６０００部となる。
【００４０】
一方、別の反応釜に、７００部の水と硫酸コバルト１３７部を溶解しておき、先の混合モノアゾ染料（Ｂ及びＣ）の溶液中へ１時間を要して注入後、８０℃、ｐＨ１０〜１１で３０分間攪拌し、コバルト化を完了させる。終点の確認は、薄層クロマトグラフ、液体クロマトグラフにより未反応モノアゾ染料が３％以下となる点とした。
【００４１】
次いで、塩析、濾過、洗浄して目的とするコバルト錯塩染料の湿ケーキ２１００部（乾燥重量約５９０部）を得た。この染料はλｍａｘ ５７０ｎｍ（ｐＨ＝７の緩衝液中）であり、水に良く溶解して鮮明紫色を呈する。また、この染料は、本発明の非対称型１：２コバルト染料を主成分とし、他にモノアゾ染料（Ｂ）の対称型１：２コバルト染料及びモノアゾ染料（Ｃ）の対称型１：２コバルト染料をそれぞれ約２０重量％を含有する混合染料である。[Industrial applications]
The present invention relates to a cobalt-containing azo compound, a method for dyeing a polyamide fiber material using the same, and a method for producing the cobalt-containing azo compound.
[0002]
[Prior art]
Conventionally, chromium or cobalt complex salts of monoazo dyes have excellent dyeing properties for synthetic or natural polyamide fibers and materials, and are widely used because of, for example, excellent hue, sharpness, wet fastness, and light fastness. It is used.
For example, Japanese Patent Publication No. Sho 42-5340, Japanese Patent Publication No. Sho 46-2428, Japanese Patent Application Laid-Open No. 58-5365, Japanese Patent Application Laid-Open No. 60-88186, Japanese Patent Application Laid-Open No. 62-225563, etc. Cobalt complex monoazo dyes are described.
[0003]
[Problems to be solved by the invention]
However, in the dyeing of polyamide artificial leather, which has been actively processed in recent years, there are few dyes that dye at a high concentration in a clear navy blue or rubin color, and in particular, the color value is high, and the sharpness of various fastnesses is excellent. A strong blue to purple dye has been strongly demanded.
The present invention completely satisfies these needs by using a cobalt-containing azo dye having a specific structure.
[0004]
[Means for Solving the Problems]
The present invention provides a compound represented by the general formula (4):
[0005]
Embedded image

[0006]
(In the formula, X and Y each independently represent a hydrogen atom, a nitro group, a chloro atom, a methyl group, an ethyl group, a sulfamoyl group, a methoxy group or an ethoxy group. R ₁ , R ₂ , and R ₃ each independently represent a carbon atom. R represents a hydrogen atom or a methyl group, Z represents a hydrogen atom, a nitro group, a chloro atom, a methyl group, an ethyl group, a sulfamoyl group, a methoxy group or an ethoxy group. , M represents hydrogen or a cationic residue.)
[0007]
And a method for producing the same and a method for dyeing a synthetic or natural polyamide fiber material using the same.
A feature of the invention is based on the observation that valuable cobalt-containing azo dyes are obtained by complexing one molecule of cobalt with two different monoazo dye molecules.
[0008]
The production of the valuable cobalt-containing azo dye represented by the general formula (4) of the present invention is performed, for example, by the following method.
General formula (1)
[0009]
Embedded image

[0010]
(In the formula, X and Y each independently represent a hydrogen atom, a nitro group, a chloro atom, a methyl group, an ethyl group, a sulfamoyl group, a methoxy group or an ethoxy group. R ₁ and R ₂ each independently represent a carbon atom of 1 to 1. 4 represents a lower alkyl group, and R represents a hydrogen atom or a methyl group.)
And a monoazo dye represented by the formula (2) or (3):
[0011]
Embedded image

[0012]
Embedded image

[0013]
(In the above formula, Q and Z each independently represent a hydrogen atom, a nitro group, a chloro atom, a methyl group, an ethyl group, a sulfamoyl group, a methoxy group or an ethoxy group. R ₃ is lower alkyl having 1 to 4 carbon atoms. Represents a group.)
With a monoazo dye represented by the formula (1), by acting a cobalt imparting agent such that one atom of cobalt is complex-bonded to one molecule of each monoazo dye.
[0014]
Examples of the monoazo dye represented by the general formula (1) include 3- (dimethylamino) phenol, 3- (diethylamino) phenol, 3- (dibutylamino) phenol, 3- (dipropylamino) phenol, and 3- (diethylamino) phenol. ) Phenol, 3- (dimethylamino) -4-methylphenol, 3- (diethylamino) -4-methylphenol, 3- (dibutylamino) -4-methylphenol and diazotized 2-amino-phenol, -Amino-4-nitrophenol, 2-amino-5-nitrophenol, 2-amino-4-chlorophenol, 2-amino-4-methylphenol, 2-amino-4-methoxyphenol, 2-amino-4- Chloro-6-nitro-phenol, 2-amino-4-nitro-6-chloro-phenol, 2 Amino-4-methyl-6-nitro - such as the weakly acidic phenolic easily be obtained by a coupling reaction with a neutral or weakly alkaline medium.
[0015]
The monoazo dye represented by the general formula (2) or (3) includes, for example, 6-amino-N-methyl-2-naphthalenesulfonamide, 6-amino-N-ethyl-2-naphthalenesulfonamide, 6-amino -N-propyl-2-naphthalenesulfonamide, 6-amino-N-butyl-2-naphthalenesulfonamide, 6-hydroxy-N-methyl-2-naphthalenesulfonamide, 6-hydroxy-N-ethyl-2-naphthalene Sulfonamide, 6-hydroxy-N-propyl-2-naphthalenesulfonamide, 6-hydroxy-N-butyl-2-naphthalenesulfonamide, diazotized 2-amino-phenol, 2-amino-4-nitrophenol , 2-amino-5-nitrophenol, 2-amino-4-chlorophenol, 2-amino- -Methylphenol, 2-amino-4-methoxyphenol, 2-amino-4-chloro-6-nitro-phenol, 2-amino-4-chloro-5-nitrophenol, 2-amino-4-nitro-6- Chlorophenol and 2-amino-4-methyl-6-nitro-phenol can be easily produced by a coupling reaction with 2-amino-4,6 dinitrophenol.
[0016]
The present invention is characterized in that it is a so-called asymmetric type cobalt complex dye in which one molecule of cobalt is complex-bonded to two molecules of different monoazo dyes. A so-called symmetric cobalt complex dye in which atoms are complex-bonded, that is, a 1: 2 cobalt dye of the general formula (1), a 1: 2 cobalt dye of the general formula (2) or a 1: 2 cobalt dye of the general formula (3) Is produced, and these symmetrical cobalt complex dyes may be contained in a considerable ratio. However, even such a mixed dye may give favorable results for dyeing polyamide fibers and is included in the present invention.
[0017]
As another method for producing the cobalt-containing azo compound represented by the general formula (4), which is an object of the present invention, each method for synthesizing the monoazo dye represented by the general formula (1) and the general formula (2) or (3) The components (diazo component, coupling component) and the cobalt-imparting agent are mixed in an arbitrary order, for example, at least one obtained by reacting a diazotized product of at least one diazo component with a mixture of at least two coupling components. A method of simultaneously producing a monoazo compound represented by the general formula (4) by causing a cobalt imparting agent to act on a monoazo dye mixture containing no two metals is considered. This method can simplify the process and can be an industrially advantageous manufacturing method.
[0018]
The monoazo dyes used in the process according to the invention are preferably used in the subsequent processing in the form of a wet paste without drying after their synthesis and precipitation.
Next, a known method is applied to the reaction between the monoazo dye and the cobalt-imparting agent. For example, these monoazo dyes are dissolved in water or an aqueous medium such as methanol, acetone, glycols or the like with respect to the monoazo dye base. The reaction is carried out at a temperature of 70 to 110 ° C, preferably 90 to 95 ° C, using a cobalt imparting agent in a molar ratio of 0.51 to 0.6.
[0019]
Here, as the cobalt imparting agent, for example, cobalt sulfate, cobalt tartrate, cobalt acetate and the like are used.
At this time, an organic amine such as alkanolamine and an alkaline agent such as caustic soda and soda ash can be used as a catalyst for cobaltation.
[0020]
The better the molar ratio of the diazo compound and the coupling component in the production of the monoazo dye of the present invention is, the closer the ratio is to about 1: 1. The preferred ratio is from 1: 1 to 1.1.
The target cobalt-containing azo dye represented by the general formula (4) obtained by the method of the present invention is taken out by salting out, filtration, drying, spray drying in an aqueous solution, or as necessary. After concentration, an organic solvent is added, and it can be subjected to staining in the form of a concentrated aqueous solution.
[0021]
The cobalt-containing azo dyes obtained by the process according to the invention are suitable for dyeing and printing a great variety of substances. In particular, the compounds are suitable for dyeing animal substances, such as silk, leather, especially wool, but are also suitable for dyeing and printing synthetic fiber materials made from polyamides, polyurethanes and the like. Particularly, it has a high color value with respect to polyamide-based synthetic leather and suede materials, and is suitable for dyeing a clear blue or purple color having excellent fastnesses.
[0022]
The cobalt-containing azo dyes obtained by the process of the present invention can be dyed from weakly alkaline to slightly acidic baths, but are particularly successful when applied from neutral or slightly acidic baths containing, for example, acetic acid or ammonium sulfate. Is obtained. The dyed product thus obtained is uniform and shows good fastness to sunlight, washing and the like, but is particularly excellent in its sharpness and build-up property.
[0023]
【The invention's effect】
The cobalt-containing azo dyes of the invention are particularly suitable for dyeing animal substances, such as silk, leather, especially wool, but also for dyeing and printing synthetic fiber materials made from polyamides, polyurethanes and polyacrylonitriles. I have. In addition, it is dyed in a clear blue or purple color having high color value and excellent fastness to polyamide-based synthetic leather, particularly to a suede-like material.
[0024]
【Example】
The present invention will be specifically described by the following examples. In the examples, parts represent parts by weight.
[0025]
Example 1
In a diazotization reactor, 1200 parts of water, 92.5 parts of 2-amino-5-nitro-1-hydroxybenzene and 56.5 parts of 47% by weight of caustic soda are dissolved with stirring. Next, 87 parts of 100% by weight sulfuric acid and 480 parts of ice were added, and the mixture was cooled to 3 to 5 ° C., and 116 parts of 36% by weight of sodium nitrite was poured in about 30 minutes, and the mixture was heated at 5 to 10 ° C. for 1 hour. Stir to complete diazotization.
[0026]
In a coupling reactor, 1000 parts of water and 148.6 parts of 2-aminonaphthalene-6-sulfonic acid-N-methylamide are charged and well dispersed. After adding 320 parts of ice and cooling to 20 ° C., pour the mixture into the above-mentioned diazotization reaction vessel in 30 minutes, add a dispersant (QMC 41% product, 200 parts) and add several parts at 10 to 20 ° C. Stir for hours. During this time, the pH is adjusted to be maintained at 0.5 to 1.5.
After filtration and washing, about 800 parts (236 parts by dry weight) of a wet cake (A) of a monoazo dye was obtained.
[0027]
On the other hand, 1400 parts of water and 146 parts of 36% by weight hydrochloric acid were added to another diazotization reactor, and 107.8 parts of 2-amino-5-nitro-1-hydroxybenzene was added thereto. Disperse, add 700 parts of ice and cool to 3-5 ° C. To this, 139 parts of 36% by weight sodium nitrite was poured in about 30 minutes, and the mixture was stirred at 5 to 10 ° C. for 1 hour to complete diazotization, and adjusted to pH 4 to 5 by adding 70 parts of sodium acetate. I do.
[0028]
Next, 2800 parts of water, 117 parts of 1-hydroxy-3-diethylaminobenzene and 71 parts of 47% by weight caustic soda were charged and stirred and dissolved in a coupling reactor, and 140 parts of soda ash and 900 parts of ice were further dissolved. Add.
Next, the above-mentioned diazotized solution is poured into this for about 30 minutes, and the coupling reaction is completed at a temperature of 15 to 20 ° C. and a pH of 10 to 10.5 over several hours.
After salting out, filtration and washing, about 700 parts (dry weight: 210 parts) of a wet cake (B) of a monoazo dye was obtained.
[0029]
[Cobaltization]
5000 parts of water, the above-mentioned monoazo dye (A) (211 parts in terms of dry weight) and 55 parts of 47% by weight caustic soda are added to a reaction vessel, adjusted to pH 12 to 12.5, and dissolved by heating. The residue is filtered off, and then a monoazo dye (B) (176 parts in terms of dry weight) and 50 parts of diethanolamine are added, and the temperature is raised to 90 to 95 ° C.
On the other hand, 1500 parts of water and 225 parts of soda ash are dissolved in another reactor. Further, 600 parts of water, 141 parts of cobalt sulfate and 80 parts of tartaric acid were added to and dissolved in another reaction vessel, and these two aqueous solutions were poured into the mixed monoazo dye in one hour in parallel to carry out cobaltation. Let it complete.
[0030]
Subsequently, salting out, filtration, washing and drying were performed to obtain 587 parts of the desired cobalt-containing azo dye. This dye has a λmax of 584 nm (in a buffer solution of pH = 7) and dissolves well in water to give a reddish clear blue color. This dye is mainly composed of the asymmetrical 1: 2 cobalt dye of the present invention, and is also a symmetrical 1: 2 cobalt dye of the monoazo dye (A) and a symmetrical 1: 2 cobalt dye of the monoazo dye (B). Are mixed dyes each containing about 20% by weight.
[0031]
[Staining Example 1]
0.1 g of the dye obtained by the above method was dissolved in 100 g of water, put into a dyeing pot of a mini-color dyeing tester, and 2.0 g of suede-like polyamide artificial leather was put into the pot and the lid was closed. This dyeing pot was inserted into a mini-color dyeing machine having an internal temperature of 40 ° C., and the temperature was raised to 90 ° C. in 50 minutes. After keeping the temperature at 90 ° C. for 30 minutes, the dyeing pot is taken out and cooled. The material to be dyed was taken out and washed according to a conventional method. The dyed product thus obtained exhibited a clear navy blue color and good fastnesses.
[0032]
[Staining Example 2]
0.1 g of the dye obtained by the above method was dissolved in 300 g of water, put into a dyeing pot of a color pet dyeing machine, and 5.0 g of nylon spun yarn and 0.15 g of ammonium sulfate were added thereto. Dyeing was started from 40 ° C., the temperature was raised to 100 ° C. in 60 minutes, and the temperature was kept at 100 ° C. for 10 minutes. Then, 0.5 ml of 10% acetic acid was added, and the temperature was further kept for 20 minutes. Thereafter, the material to be dyed was taken out and washed according to a conventional method. The dyed product thus obtained exhibited a clear navy color and had various fastnesses.
[0033]
Examples 1 to 17
In the same manner as in Example 1, the monoazo dyes (Nos. 2 to 17) shown in Tables 1 and 2 below were used as the monoazo dyes of the general formula (1) used in Example 1. As a result, a cobalt-containing azo dye having excellent dyeability having the following hue was obtained. Table 1 shows that the dye of Example 1 was No. 1 as well. Also described as 1.
[0034]
[Table-1]

[0035]
[Table-2]

[0036]
Example 18
In a diazotization reactor, 1200 parts of water, 92.5 parts of 2-amino-5-nitro-1-hydroxybenzene and 56.5 parts of 47% by weight of caustic soda are dissolved with stirring. Next, 87 parts of 100% by weight sulfuric acid and 480 parts of ice were added, and the mixture was cooled to 3 to 5 ° C., and 116 parts of 36% by weight of sodium nitrite was poured in about 30 minutes, and the mixture was heated at 5 to 10 ° C. for 1 hour. Stir to complete diazotization.
[0037]
In a coupling reactor, 1500 parts of water, 149.2 parts of 2-hydroxynaphthalene-6-sulfonic acid-N-methylamide, 127.4 parts of 47% by weight of caustic soda and 64 parts of soda ash are stirred and melted, and then iced. Cool to 0-5 ° C with 800 parts. The above diazotization reaction solution is injected into this in about 30 minutes. The liquid temperature becomes 5 to 10 ° C and the pH becomes 12 to 12.5.
[0038]
Thereafter, hydrochloric acid aqueous solution prepared by diluting 50 parts of 35% by weight hydrochloric acid with 25 parts of water was added to adjust the pH to 11 to 11.5 and stirred for 10 to 15 hours. Then, 30 parts of 35% by weight hydrochloric acid was diluted with 15 parts of water. The pH is adjusted to 9.5 to 10 with hydrochloric acid. The liquid volume is about 6500 parts.
After confirming the end point of the coupling reaction (confirmed no color development with an aqueous ammonia solution of resorcinol), the temperature was raised to 70 ° C., 650 parts of industrial salt was added, salted out, filtered, washed, and about 1000 parts of wet cake (dried) A wet cake (C) of a monoazo dye having a weight of 192 parts) was obtained. Yield about 80%.
[0039]
[Cobaltization]
5000 parts of water, the monoazo dye (B) (176 parts in terms of dry weight) obtained in Example 1 and the monoazo dye (C) (192 parts in terms of dry weight) obtained by the above method were added to a reaction vessel. 85 parts of 47% by weight caustic soda and 106 parts of soda ash are added, and the temperature is raised to 75 to 80 ° C. The liquid volume becomes about 6000 parts.
[0040]
On the other hand, 700 parts of water and 137 parts of cobalt sulfate were dissolved in another reaction vessel, and the mixture was poured into the solution of the mixed monoazo dyes (B and C) in 1 hour, and then 80 ° C., pH 10 Stir at １１11 for 30 minutes to complete the cobaltation. The end point was confirmed by a thin layer chromatography and a liquid chromatography at a point where the amount of the unreacted monoazo dye was 3% or less.
[0041]
Next, salting out, filtration, and washing were performed to obtain 2100 parts (dry weight: about 590 parts) of the desired wet cake of the cobalt complex salt dye. This dye has a λmax of 570 nm (in a buffer solution at pH = 7) and is well dissolved in water to give a clear purple color. The dye is mainly composed of the asymmetric 1: 2 cobalt dye of the present invention, and is also a symmetric 1: 2 cobalt dye of a monoazo dye (B) and a symmetric 1: 2 cobalt dye of a monoazo dye (C). Are mixed dyes each containing about 20% by weight.

Claims (4)

The following general formula (4)

(In the formula, X and Y each independently represent a hydrogen atom, a nitro group, a chloro atom, a methyl group, an ethyl group, a sulfamoyl group, a methoxy group or an ethoxy group. R ₁ , R ₂ , and R ₃ each independently represent a carbon atom. R represents a hydrogen atom or a methyl group, and Q and Z each independently represent a hydrogen atom, a nitro group, a chloro atom, a methyl group, an ethyl group, an ethyl group, a sulfamoyl group, a methoxy group or an ethoxy group. A represents -NH- or -O-, and M represents hydrogen or a cation residue.)
A cobalt-containing azo compound represented by the formula: General formula (1)

(In the formula, X and Y each independently represent a hydrogen atom, a nitro group, a chloro atom, a methyl group, an ethyl group, a sulfamoyl group, a methoxy group or an ethoxy group. R ₁ and R ₂ each independently represent a carbon atom of 1 to 1. 4 represents a lower alkyl group, and R represents a hydrogen atom or a methyl group.)
And a monoazo dye represented by the formula (2) or (3):

(In the above formula, Q and Z each independently represent a hydrogen atom, a nitro group, a chloro atom, a methyl group, an ethyl group, a sulfamoyl group, a methoxy group or an ethoxy group. R ₃ is lower alkyl having 1 to 4 carbon atoms. Represents a group.)
A monoazo dye represented by the general formula (4), wherein a cobalt imparting agent is acted on such that one atom of cobalt is complex-bonded to one molecule of each monoazo dye.

(Wherein, X, Y, R, R ₁ , R ₂ , R ₃ , Q and Z have the above-mentioned meanings, A represents —NH— or —O—, and M represents hydrogen or a cation. Represents a residue.)
A method for producing a cobalt-containing azo dye represented by the formula: The following general formula (4)

(In the formula, X and Y each independently represent a hydrogen atom, a nitro group, a chloro atom, a methyl group, an ethyl group, a sulfamoyl group, a methoxy group or an ethoxy group. R ₁ , R ₂ , and R ₃ each independently represent a carbon atom. R represents a hydrogen atom or a methyl group, and Q and Z each independently represent a hydrogen atom, a nitro group, a chloro atom, a methyl group, an ethyl group, an ethyl group, a sulfamoyl group, a methoxy group or an ethoxy group. Represents a group, and M represents a hydrogen or a cation residue.)
A method for dyeing a polyamide fiber material, comprising dyeing a synthetic or natural polyamide fiber material with the use of a cobalt-containing azo dye represented by the formula: The method for dyeing a polyamide fiber material according to claim 3, which is used for dyeing a polyamide artificial leather.
[0001]